TWI403269B - Piperazine compounds having herbicidal action - Google Patents

Piperazine compounds having herbicidal action Download PDF

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TWI403269B
TWI403269B TW096100345A TW96100345A TWI403269B TW I403269 B TWI403269 B TW I403269B TW 096100345 A TW096100345 A TW 096100345A TW 96100345 A TW96100345 A TW 96100345A TW I403269 B TWI403269 B TW I403269B
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compounds
formula
alkyl
group
compound
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TW096100345A
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TW200803732A (en
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Eike Hupe
Cyrill Zagar
Matthias Witschel
Toralf Kuehn
William Karl Moberg
Rapado Liliana Parra
Frank Stelzer
Andrea Vescovi
Robert Reinhard
Bernd Sievernich
Klaus Grossmann
Thomas Ehrhardt
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Basf Ag
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/10—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D241/14—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D241/18—Oxygen or sulfur atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • A01N37/46—N-acyl derivatives
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/60—1,4-Diazines; Hydrogenated 1,4-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
    • A01N43/647—Triazoles; Hydrogenated triazoles
    • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
    • C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
    • C07D241/06—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having one or two double bonds between ring members or between ring members and non-ring members
    • C07D241/08—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having one or two double bonds between ring members or between ring members and non-ring members with oxygen atoms directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms

Abstract

The present invention relates to the use of piperazine compounds of the formula I or of the agriculturally useful salts of piperazine compounds of the formula I as herbicides, where in formula I the variables are as defined in the claims and the description. Moreover, the invention relates to compositions comprising, in addition to auxiliaries customary for formulating crop protection agents, piperazine compounds of the formula I or agriculturally useful salts of I, and to a process for preparing these compositions. Furthermore, the invention relates to certain piperazine compounds of the formula I, a process for preparing piperazine compounds of the formula I and a method for controlling unwanted vegetation which comprises treating plants, their seeds and/or their habitat with at least one piperazine compound of the formula I.

Description

具有除草作用之哌 化合物Piperidic compound with herbicidal action

本發明係關於具有除草作用之哌化合物。The present invention relates to a herbicide having a herbicidal action Compound.

由植物病原菌瘡痂菌(S.scabies)產生之疥鏈黴菌素(thaxtomins)A與B(King R.R.等人之J.Agric.Food Chem.(1992)40,834－837)為一種天然產物，其具有一個中心哌－2,5－二酮環，於3－位置帶有4－硝基吲哚－3－基甲基，2－位置上帶有可視需要經OH取代之苯甲基。由於其具有傷害植物之作用，因此亦探討此類化合物作為除草劑之用途可能性(King R.R.等人之J.Agric.Food Chem.(2001)49,2298－2301)。Thaxtomins A and B produced by the phytopathogenic S. scabies (King RR et al. J. Agric. Food Chem. (1992) 40, 834-837) is a natural product having a Central piper a -2,5-dione ring having a 4-nitroindol-3-ylmethyl group at the 3-position with a benzyl group optionally substituted with OH at the 2-position. Because of its role in harming plants, the use of such compounds as herbicides is also explored (King Agri et al., J. Agric. Food Chem. (2001) 49, 2298-2301).

有關疥鏈黴菌素(thaxtomins)A與B製法之合成研究中，J.Gelin等人之J.Org.Chem.58,1993,pp.3473－3475與J.Moyroud等人之Tetrahedron 52,1996,pp.8525－8543說明脫氫疥鏈黴菌素衍生物。其中特別說明如下式化合物 其中R為氫或NO2 。For the synthesis of thaxtomins A and B, J. Gelin et al., J. Org. Chem. 58, 1993, pp. 3473-3475 and J. Moyroud et al., Tetrahedron 52, 1996, Pp. 8525-8543 illustrates a dehydrogenated streptavidin derivative. Specifically, the following formula Wherein R is hydrogen or NO 2 .

N.Saito等人之J.Chem.Soc.Perkin Trans 1997,pp.53－69特別說明如下式化合物 其中Ry 為氫或苯甲基與Rx 為氫、乙醯基或異丙基氧羰基，作為製備海鞘素(ecteinascidins)之前體。J. Chem. Soc. Perkin Trans 1997, pp. 53-69 by N. Saito et al. Wherein R y is hydrogen or benzyl and R x is hydrogen, acetyl or isopropyloxycarbonyl, as a precursor for the preparation of ecteinascidins.

在製備弗希汀(phthalascidin)之相關合成研究中，Z.Z.Liu等人在Chinese Chem.Lett.13(8)2002,pp.701－704中說明如下式中間物，其中Bn為苯甲基： In the related synthetic studies for the preparation of phthalascidin, ZZ Liu et al., Chinese Chem. Lett. 13 (8) 2002, pp. 701-704, describe intermediates of the formula wherein Bn is benzyl:

J.Bryans等人在Journal of Antibiotics 49(10),1996,pp.1014－1021中說明如下式化合物： J. Bryans et al., in Journal of Antibiotics 49 (10), 1996, pp. 1014-1021, describe compounds of the formula:

WO 99/48889、WO 01/53290與WO 2005/011699說明2,5－二酮基哌化合物，其在3－與6－位置上利用亞甲基或次甲基(methyne)附接4－咪唑基且在另一個3－或6－位置上利用苯甲基或亞苯甲基附接。此等化合物為抗腫瘤化合物。WO 99/48889, WO 01/53290 and WO 2005/011699 describe 2,5-diketopiperyl a compound that attaches to a 4-imidazolyl group using a methylene or methyne at the 3- and 6-positions and a benzyl or phenylene group at another 3- or 6-position . These compounds are anti-tumor compounds.

本發明係有關以式I哌化合物 或式I哌化合物之農業上適用之鹽作為除草劑之用途，其中式I之代號定義如下：R1 與R2 分別獨立為：氰基、C1 －C6 －烷基、C3 －C6 －環烷基、C3 －C6 －烯基、C3 －C6 －環烯基、C3 －C6 －炔基、C3 －C6 －環炔基、苯基、苯基－(C1 －C6 )－烷基、雜環基、雜環基－(C1 －C6 )－烷基；苯基－[C1 －C6 －烷氧基羰基]－(C1 －C6 )－烷基或苯基雜環基－(C1 －C6 )－烷基；或COR21 ，其中R21 為氫、C1 －C6 －烷基、C3 －C6 －環烷基、C2 －C6 －烯基、C3 －C6 －環烯基、C2 －C6 －炔基、C3 －C6 －環炔基、羥基、C1 －C6 －烷氧基、C3 －C6 －烯基氧、C3 －C6 －炔基氧、胺基、C1 －C6 －烷基胺基、[二－(C1 －C6 )－烷基]胺基、C3 －C6 －烯基胺基、C3 －C6 －炔基胺基、C1 －C6 －烷基磺醯基胺基、N－(C2 －C6 －烯基)－N－(C1 －C6 －烷基)胺基、N－(C2 －C6 －炔基)－N－(C1 －C6 －烷基)胺基、N－(C1 －C6 －烷氧基)－N－(C1 －C6 －烷基)胺基、N－(C2 －C6 －烯基)－N－(C1 －C6 －烷氧基)胺基、N－(C2 －C6 －炔基)－N－(C1 －C6 －烷氧基)胺基、苯基、苯基胺基、苯氧基、萘基或雜環基；或NR22 R23 ，其中R22 與R23 分別獨立為氫、C1 －C6 －烷基、C3 －C6 －環烷基、C3 －C6 －烯基、C3 －C6 －環烯基、C3 －C6 －炔基、C3 －C6 －環炔基或C1 －C6 －烷基羰基；或OR24 ，其中R24 為C1 －C6 －烷基、C3 －C6 －環烷基、C3 －C6 －烯基、C3 －C6 －環烯基、C3 －C6 －炔基、C3 －C6 －環炔基、苯基或苯基－(C1 －C6 )－烷基；或SO2 R25 ，其中R25 為C1 －C6 －烷基或苯基；其中R1 與R2 之取代基之如上述脂系、環狀或芳香系部份基團可部份或完全鹵化與/或可帶有1至3個下列基團：氰基、羥基、C1 －C4 －烷基、C1 －C4 －鹵烷基、C3 －C6 －環烷基、C1 －C4 －烷氧基、C1 －C4 －烷基硫、[二－(C1 －C4 )－烷基]胺基、C1 －C4 －烷基羰基、羥基羰基、C1 －C4 －烷氧基羰基、胺基羰基、C1 －C4 －烷基胺基羰基、[二－(C1 －C4 )－烷基]胺基羰基或C1 －C4 －烷基羰基氧；且其中R1 亦可為氫；R3 為氫、鹵素、氰基、C1 －C6 －烷基、C3 －C6 －環烷基、C2 －C6 －烯基、C3 －C6 －環烯基、C2 －C6 －炔基、C3 －C6 －環炔基、苯基、苯基－(C1 －C6 )－烷基、雜環基、雜環基－(C1 －C6 )－烷基；苯基－[C1 －C6 －烷氧基羰基]－(C1 －C6 )－烷基或苯基雜環基－(C1 －C6 )－烷基；或基團COR26 、NR27 R28 、OR29 、SO2 R30 或N(OR31 )R32 ，其中R26 為氫、C1 －C6 －烷基、C3 －C6 －環烷基、C2 －C6 －烯基、C3 －C6 －環烯基、C2 －C6 －炔基、C3 －C6 －環炔基、羥基、C1 －C6 －烷氧基、C3 －C6 －烯基氧、C3 －C6 －炔基氧、胺基、C1 －C6 －烷基胺基、[二－(C1 －C6 )－烷基]胺基、C3 －C6 －烯基胺基、C3 －C6 －炔基胺基、C1 －C6 －烷基磺醯基胺基、N－(C2 －C6 －烯基)－N－(C1 －C6 －烷基)胺基、N－(C2 －C6 －炔基)－N－(C1 －C6 －烷基)胺基、N－(C1 －C6 －烷氧基)－N－(C1 －C6 －烷基)胺基、N－(C2 －C6 －烯基)－N－(C1 －C6 －烷氧基)胺基、N－(C2 －C6 －炔基)－N－(C1 －C6 －烷氧基)胺基、苯基、苯基胺基、苯氧基、萘基或雜環基；R27 與R28 分別獨立為氫、C1 －C6 －烷基、芳基或雜芳基；R29 為C1 －C6 －烷基；R30 為C1 －C6 －烷基或苯基；R31 為氫、C1 －C6 －烷基、苯基或苯基－(C1 －C6 )－烷基；R32 為C1 －C6 －烷基、苯基或苯基－(C1 －C6 )－烷基；其中R3 或R26 、R27 、R28 、R29 、R30 、R31 與R32 之取代基之如上述脂系、環狀或芳香系部份基團可部份或完全鹵化與/或可帶有1至3個下列基團：氰基、羥基、C1 －C4 －烷基、C1 －C4 －鹵烷基、C3 －C6 －環烷基、C1 －C4 －烷氧基、C1 －C4 －烷基硫、[二－(C1 －C4 )－烷基]胺基、C1 －C4 －烷基羰基、羥基羰基、C1 －C4 －烷氧基羰基、胺基羰基、C1 －C4 －烷基胺基羰基、[二－(C1 －C4 )－烷基]胺基羰基或C1 －C4 －烷基羰基氧；R4 、R5 、R6 分別獨立為氫、羥基、C1 －C6 －烷基、C1 －C6 －烷氧基，其中R4 、R5 或R6 之取代基之如上述脂系部份基團可部份或完全鹵化與/或可帶有1至3個下列基團：氰基、羥基、C1 －C4 －烷基、C1 －C4 －鹵烷基、C3 －C6 －環烷基、C1 －C4 －烷氧基、C1 －C4 －烷基硫、[二－(C1 －C4 )－烷基]胺基、C1 －C4 －烷基羰基、羥基羰基、C1 －C4 －烷氧基羰基、胺基羰基、C1 －C4 －烷基胺基羰基、[二－(C1 －C4 )－烷基]胺基羰基或C1 －C4 －烷基羰基氧；A1 為芳基或雜芳基；A2 為芳基或雜芳基，但吲哚基除外；Ra 為鹵素、氰基、硝基、C1 －C6 －烷基、C3 －C6 －環烷基、C2 －C6 －烯基、C3 －C6 －環烯基、C4 －C10 －烷二烯基、C2 －C6 －炔基、[三－(C1 －C6 )－烷基矽烷基]－(C2 －C6 )－炔基、C3 －C6－環炔基、C1 －C6 －烷基硫、C1 －C6 －烷基亞磺醯基、芳基、苯基－(C1 －C6 )－烷基、苯基－(C2 －C6 )－烯基、苯基磺醯基－(C1 －C6 )－烷基、雜環基、雜環基－(C1 －C6 )－烷基或苯基－[C1 －C6 －烷氧基羰基]－(C1 －C6 )－烷基，Z1 P(O)(OR9 )2 、Z2 B(OR10 )2 ，其中R9 與R10 分別為氫或C1 －C6 －烷基，且Z2 B(OR10 )2 中之基團R10 共同形成C2 －C4 －伸烷基鏈；或Z3 COR11 ，其中R11 為氫、C1 －C6 －烷基、C3 －C6 －環烷基、C2 －C6 －烯基、C3 －C6 －環烯基、C2 －C6 －炔基、C3 －C6 －環炔基、羥基、C1 －C6 －烷氧基、C3 －C6 －烯基氧、C3 －C6 －炔基氧、胺基、C1 －C6 －烷基胺基、[二－(C1 －C6 )－烷基]胺基、C1 －C6 －烷氧基胺基、[二－(C1 －C6 )－烷氧基]胺基、C1 －C6 －烷基磺醯基胺基、C1 －C6 －烷基胺基磺醯基胺基、[二－(C1 －C6 )－烷基胺基]磺醯基胺基、C3 －C6 －烯基胺基、C3 －C6 －炔基胺基、N－(C2 －C6 －烯基)－N－(C1 －C6 －烷基)胺基、N－(C2 －C6 －炔基)－N－(C1 －C6 －烷基)胺基、N－(C1 －C6 －烷氧基)－N－(C1 －C6 －烷基)胺基、N－(C2 －C6 －烯基)－N－(C1 －C6 －烷氧基)胺基、N－(C2 －C6 －炔基)－N－(C1 －C6 －烷氧基)胺基、苯基、苯氧基、苯基胺基、萘基或雜環基；或Z4 NR12 R13 ，其中R12 與R13 分別獨立為氫、C1 －C6 －烷基、C3 －C6 －環烷基、C3 －C6 －烯基、C3 －C6 －環烯基、C3 －C6 －炔基、C3 －C6 －環炔基、C1 －C6 －烷基羰基、C3 －C6 －環烷基羰基、[二－(C1 －C6 )－烷基胺基]羰基、C1 －C6 －烷氧基羰基、C1 －C6 －烷氧基羰基－(C1 －C6 )－烷基、C1 －C6 －烷基磺醯基、C1 －C6 －烷基胺基磺醯基、[二－(C1 －C6 )－烷基胺基]磺醯基、苯基羰基、苯基胺基羰基、苯基磺醯基、苯基磺醯基胺基羰基或雜環基羰基；或Z5 CH＝N－O－R14 ，其中R14 為氫或C1 －C6 －烷基；或Z6 OR15 ，其中R15 為氫、C1 －C6 －烷基、C3 －C6 －環烷基、C3 －C6 －烯基、C3 －C6 －環烯基、C3 －C6 －炔基、C3 －C6 －環炔基、C1 －C6 －烷基羰基、C1 －C6 －烷氧基羰基－(C1 －C6 )－烷基、[二－(C1 －C6 )－烷氧基羰基]－(C1 －C6 )－烷基、苯基或苯基－(C1 －C6 )－烷基；或Z7 SO2 R16 ，其中R16 為C1 －C6 －烷基或苯基；且其中Z1 、Z2 、Z3 、Z4 、Z5 、Z6 、Z7 分別獨立為一鍵結、－CH2 －、－CH2 －CH2 －、－O－CH(R17 )－、－S－CH(R18 )－、－S(O)－CH(R19 )－或－SO2 CH(R20 )－，且其中R17 、R18 、R19 與R20 分別獨立為氫或C1 －C6 －烷基；且其中如上述Ra 取代基之脂系、環狀或芳香系部份基團可部份或完全鹵化與/或可帶有1至3個下列基團：氰基、羥基、C1 －C4 －烷基、C1 －C4 －鹵烷基、C3 －C6 －環烷基、C1 －C4 －烷氧基、C1 －C4 －鹵烷氧基、C1 －C4 －烷基硫、[二－(C1 －C4 )－烷基]胺基、C1 －C4 －烷基羰基、羥基羰基、C1 －C4 －烷氧基羰基、胺基羰基、C1 －C4 －烷基胺基羰基、[二－(C1 －C4 )－烷基]胺基羰基或C1 －C4 －烷基羰基氧；與Rb 、Rc 、Rd 、Re 與Rf 分別獨立為氫或如上述Ra 定義之一；且其中Ra 、Rb 或Rc 中兩個附接A1 上相鄰環原子之基團或Rd 、Re 或Rf 中兩個附接A2 上相鄰環原子之基團亦可為直鏈C3 －C6 －伸烷基，其可部份或完全鹵化且可帶有1至3個下列基團：氰基、羥基、C1 －C4 －烷基、C1 －C4 －鹵烷基、C3 －C6 －環烷基、C1 －C4 －烷氧基、C1 －C4 －烷基硫、[二－(C1 －C4 )－烷基]胺基、C1 －C4 －烷基羰基、羥基羰基、C1 －C4 －烷氧基羰基、胺基羰基、C1 －C4 －烷基胺基羰基、[二－(C1 －C4 )－烷基]胺基羰基或C1 －C4 －烷基羰基氧，其中C3 －C6 －伸烷基中一個CH2 基團可被一羰基、硫羰基或磺醯基置換，且C3 －C6 －伸烷基中一或二個相鄰CH2 基團可分別被氧或硫或基團NR34 置換，其中R34 如上述R12 定義之一。The invention relates to the formula I Compound I The use of the agriculturally acceptable salt of the compound as a herbicide, wherein the code of the formula I is defined as follows: R 1 and R 2 are each independently: cyano, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkane , C 3 -C 6 -alkenyl, C 3 -C 6 -cycloalkenyl, C 3 -C 6 -alkynyl, C 3 -C 6 -cycloalkynyl, phenyl, phenyl-(C 1 - C 6 )-alkyl, heterocyclic, heterocyclyl-(C 1 -C 6 )-alkyl; phenyl-[C 1 -C 6 -alkoxycarbonyl]-(C 1 -C 6 )- An alkyl or phenylheterocyclyl-(C 1 -C 6 )-alkyl group; or COR 21 , wherein R 21 is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 2- C 6 -alkenyl, C 3 -C 6 -cycloalkenyl, C 2 -C 6 -alkynyl, C 3 -C 6 -cycloalkynyl, hydroxy, C 1 -C 6 -alkoxy, C 3- C 6 -alkenyloxy, C 3 -C 6 -alkynyloxy, amine, C 1 -C 6 -alkylamino, [di-(C 1 -C 6 )-alkyl]amine, C 3 -C 6 -alkenylamino, C 3 -C 6 -alkynylamino, C 1 -C 6 -alkylsulfonylamino, N-(C 2 -C 6 -alkenyl)-N - (C 1 -C 6 - alkyl) amino, N- (C 2 -C 6 Alkynyl) -N- (C 1 -C 6 - alkyl) amino, N- (C 1 -C 6 - alkoxy) -N- (C 1 -C 6 - alkyl) amino, N- (C 2 -C 6 -alkenyl)-N-(C 1 -C 6 -alkoxy)amino, N-(C 2 -C 6 -alkynyl)-N-(C 1 -C 6 -alkane Oxy)amino, phenyl, phenylamino, phenoxy, naphthyl or heterocyclic; or NR 22 R 23 wherein R 22 and R 23 are independently hydrogen, C 1 -C 6 -alkyl , C 3 -C 6 -cycloalkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -cycloalkenyl, C 3 -C 6 -alkynyl, C 3 -C 6 -cycloalkynyl or C 1 -C 6 -alkylcarbonyl; or OR 24 , wherein R 24 is C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -alkenyl, C 3 -C 6 a cycloalkenyl group, a C 3 -C 6 -alkynyl group, a C 3 -C 6 -cycloalkynyl group, a phenyl group or a phenyl-(C 1 -C 6 )-alkyl group; or SO 2 R 25 , wherein R 25 Is a C 1 -C 6 -alkyl or phenyl group; wherein the substituents of R 1 and R 2 such as the above aliphatic, cyclic or aromatic moiety may be partially or completely halogenated and/or may carry 1 to three of the following groups: cyano, hydroxy, C 1 -C 4 - -alkyl, C 1 C 4 - haloalkyl, C 3 -C 6 - cycloalkyl, C 1 -C 4 - alkoxy, C 1 -C 4 - alkylthio, [di - (C 1 -C 4) - alkyl Amino, C 1 -C 4 -alkylcarbonyl, hydroxycarbonyl, C 1 -C 4 -alkoxycarbonyl, aminocarbonyl, C 1 -C 4 -alkylaminocarbonyl, [di-(C 1 -C 4 )-alkyl]aminocarbonyl or C 1 -C 4 -alkylcarbonyloxy; and wherein R 1 may also be hydrogen; R 3 is hydrogen, halogen, cyano, C 1 -C 6 -alkyl , C 3 -C 6 -cycloalkyl, C 2 -C 6 -alkenyl, C 3 -C 6 -cycloalkenyl, C 2 -C 6 -alkynyl, C 3 -C 6 -cycloalkynyl, benzene , phenyl-(C 1 -C 6 )-alkyl, heterocyclic, heterocyclyl-(C 1 -C 6 )-alkyl; phenyl-[C 1 -C 6 -alkoxycarbonyl] -(C 1 -C 6 )-alkyl or phenylheterocyclyl-(C 1 -C 6 )-alkyl; or the group COR 26 , NR 27 R 28 , OR 29 , SO 2 R 30 or N ( OR 31 )R 32 , wherein R 26 is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 2 -C 6 -alkenyl, C 3 -C 6 -cycloalkenyl, C 2 -C 6 -alkynyl, C 3 -C 6 -cycloalkynyl, hydroxy, C 1 - C 6 -alkoxy, C 3 -C 6 -alkenyloxy, C 3 -C 6 -alkynyloxy, amine, C 1 -C 6 -alkylamino, [di-(C 1 -C 6 )-alkyl]amino, C 3 -C 6 -alkenylamino, C 3 -C 6 -alkynylamino, C 1 -C 6 -alkylsulfonylamino, N-(C 2 - C 6 -alkenyl)-N-(C 1 -C 6 -alkyl)amino, N-(C 2 -C 6 -alkynyl)-N-(C 1 -C 6 -alkyl)amine, N-(C 1 -C 6 -alkoxy)-N-(C 1 -C 6 -alkyl)amino, N-(C 2 -C 6 -alkenyl)-N-(C 1 -C 6 - alkoxy)amino, N-(C 2 -C 6 -alkynyl)-N-(C 1 -C 6 -alkoxy)amino, phenyl, phenylamino, phenoxy, naphthalene Or a heterocyclic group; R 27 and R 28 are each independently hydrogen, C 1 -C 6 -alkyl, aryl or heteroaryl; R 29 is C 1 -C 6 -alkyl; R 30 is C 1 - C 6 -alkyl or phenyl; R 31 is hydrogen, C 1 -C 6 -alkyl, phenyl or phenyl-(C 1 -C 6 )-alkyl; R 32 is C 1 -C 6 -alkane group, phenyl or phenyl - (C 1 -C 6) - alkyl; wherein R 3 or R 26, R 27, R 28 , R 29, R 30, R 31 and R 32 is substituted As the above-described aliphatic-based, cyclic or aromatic-based moiety may be partially or fully halogenated and / or may carry one to three of the following groups: cyano, hydroxy, C 1 -C 4 - alkyl, C 1- C 4 -haloalkyl, C 3 -C 6 -cycloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, [di-(C 1 -C 4 )- Alkyl]amino, C 1 -C 4 -alkylcarbonyl, hydroxycarbonyl, C 1 -C 4 -alkoxycarbonyl, aminocarbonyl, C 1 -C 4 -alkylaminocarbonyl, [di-( C 1 -C 4 )-alkyl]aminocarbonyl or C 1 -C 4 -alkylcarbonyloxy; R 4 , R 5 , R 6 are each independently hydrogen, hydroxy, C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, wherein the substituent of R 4 , R 5 or R 6 as defined above may be partially or fully halogenated and/or may have from 1 to 3 of the following groups: Cyano, hydroxy, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 3 -C 6 -cycloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 - alkylthio, [di - (C 1 -C 4) - alkyl] amino, C 1 -C 4 - alkylcarbonyl, hydroxycarbonyl, C 1 -C 4 - alkoxycarbonyl, aminocarbonyl C 1 -C 4 - alkyl aminocarbonyl, [di - (C 1 -C 4) - alkyl] aminocarbonyl or C 1 -C 4 - alkylcarbonyloxy; A 1 is aryl or heteroaryl A 2 is an aryl or heteroaryl group, except for a fluorenyl group; R a is halogen, cyano, nitro, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 2 - C 6 -alkenyl, C 3 -C 6 -cycloalkenyl, C 4 -C 10 -alenadienyl, C 2 -C 6 -alkynyl,[tri-(C 1 -C 6 )-alkyldecane yl] - (C 2 -C 6) - alkynyl, C 3 -C6- cycloalkynyl, C 1 -C 6 - alkylthio, C 1 -C 6 - alkylsulfinyl acyl, aryl, benzyl -(C 1 -C 6 )-alkyl, phenyl-(C 2 -C 6 )-alkenyl, phenylsulfonyl-(C 1 -C 6 )-alkyl, heterocyclic, heterocyclic -(C 1 -C 6 )-alkyl or phenyl-[C 1 -C 6 -alkoxycarbonyl]-(C 1 -C 6 )-alkyl, Z 1 P(O)(OR 9 ) 2 , Z 2 B(OR 10 ) 2 , wherein R 9 and R 10 are each independently hydrogen or C 1 -C 6 -alkyl, and the groups R 10 in Z 2 B(OR 10 ) 2 together form C 2 - a C 4 -alkylene chain; or Z 3 COR 11 , wherein R 11 is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 2 -C 6 -alkenyl, C 3 -C 6 -cycloalkenyl, C 2 -C 6 -alkynyl, C 3 -C 6 -cycloalkynyl, hydroxy, C 1 -C 6 - alkoxy, C 3 -C 6 -alkenyloxy, C 3 -C 6 -alkynyloxy, amine, C 1 -C 6 -alkylamino, [di-(C 1 -C 6 )- Alkyl]amino, C 1 -C 6 -alkoxyamino, [di-(C 1 -C 6 )-alkoxy]amino, C 1 -C 6 -alkylsulfonylamino, C 1 -C 6 -alkylaminosulfonylamino, [di-(C 1 -C 6 )-alkylamino]sulfonylamino, C 3 -C 6 -alkenylamino, C 3- C 6 -alkynylamino, N-(C 2 -C 6 -alkenyl)-N-(C 1 -C 6 -alkyl)amino, N-(C 2 -C 6 -alkynyl) -N-(C 1 -C 6 -alkyl)amino group, N-(C 1 -C 6 -alkoxy)-N-(C 1 -C 6 -alkyl)amino group, N-(C 2 -C 6 -alkenyl)-N-(C 1 -C 6 -alkoxy)amino, N-(C 2 -C 6 -alkynyl)-N-(C 1 -C 6 -alkoxy) An amine group, a phenyl group, a phenoxy group, a phenylamino group, a naphthyl group or a heterocyclic group; or Z 4 NR 12 R 13 , wherein R 12 and R 13 are each independently hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -cycloalkenyl, C 3 -C 6 -alkynyl, C 3 -C 6 -cycloalkyne , C 1 -C 6 -alkylcarbonyl, C 3 -C 6 -cycloalkylcarbonyl, [di-(C 1 -C 6 )-alkylamino]carbonyl, C 1 -C 6 -alkoxy Carbonyl group, C 1 -C 6 -alkoxycarbonyl-(C 1 -C 6 )-alkyl group, C 1 -C 6 -alkylsulfonyl group, C 1 -C 6 -alkylaminosulfonyl group, [di-(C 1 -C 6 )-alkylamino]sulfonyl, phenylcarbonyl, phenylaminocarbonyl, phenylsulfonyl, phenylsulfonylaminocarbonyl or heterocyclylcarbonyl; Or Z 5 CH=N-O-R 14 , wherein R 14 is hydrogen or C 1 -C 6 -alkyl; or Z 6 OR 15 wherein R 15 is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -cycloalkenyl, C 3 -C 6 -alkynyl, C 3 -C 6 -cycloalkynyl, C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -alkoxycarbonyl-(C 1 -C 6 )-alkyl, [di-(C 1 -C 6 )-alkoxycarbonyl]-(C 1 -C 6 )-alkyl, phenyl or phenyl-(C 1 -C 6 )-alkyl; Or Z 7 SO 2 R 16 , wherein R 16 is C 1 -C 6 -alkyl or phenyl; and wherein Z 1 , Z 2 , Z 3 , Z 4 , Z 5 , Z 6 , Z 7 are each independently Bonding, -CH 2 -, -CH 2 -CH 2 -, -O-CH(R 17 )-, -S-CH(R 18 )-, -S(O)-CH(R 19 )- or - SO 2 CH(R 20 )-, wherein R 17 , R 18 , R 19 and R 20 are each independently hydrogen or C 1 -C 6 -alkyl; and wherein the R a substituent is a lipid or a ring Or an aromatic moiety may be partially or fully halogenated and/or may carry 1 to 3 of the following groups: cyano, hydroxy, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl , C 3 -C 6 -cycloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, C 1 -C 4 -alkylthio, [di-(C 1 -C) 4 )-Alkylamino, C 1 -C 4 -alkylcarbonyl, hydroxycarbonyl, C 1 -C 4 -alkoxycarbonyl, aminocarbonyl, C 1 -C 4 -alkylaminocarbonyl, [ Di-(C 1 -C 4 )-alkyl]aminocarbonyl or C 1 -C 4 -alkylcarbonyloxy; and R b , R c , R d , R e and R f are each independently hydrogen or as above one definition of R a; and wherein R a R b or R c is attached on two adjacent groups A 1 ring atoms or R d, a group of adjacent ring atoms, or 2 R e in R f is attached to two A may be straight-chain C 3- C 6 -alkylene which may be partially or fully halogenated and may carry 1 to 3 of the following groups: cyano, hydroxy, C 1 -C 4 -alkyl, C 1 -C 4 -halane , C 3 -C 6 -cycloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio, [di-(C 1 -C 4 )-alkyl]amine, C 1- C 4 -alkylcarbonyl, hydroxycarbonyl, C 1 -C 4 -alkoxycarbonyl, aminocarbonyl, C 1 -C 4 -alkylaminocarbonyl, [di-(C 1 -C 4 )- An alkyl]aminocarbonyl group or a C 1 -C 4 -alkylcarbonyloxy group, wherein one CH 2 group in the C 3 -C 6 -alkylene group may be replaced by a carbonyl group, a thiocarbonyl group or a sulfonyl group, and C 3 One or two adjacent CH 2 groups in the -C 6 -alkylene group may be replaced by oxygen or sulfur or a group NR 34 , respectively, wherein R 34 is as defined in the above R 12 .

本發明之目的為提供一種具有除草作用之化合物。特定言之本發明提供一種具有高度除草活性之化合物，特定言之即使在低施用率下，且其與作物植株之相容性足以供商業使用。It is an object of the present invention to provide a herbicidal compound. In particular, the present invention provides a compound having a high herbicidal activity, in particular even at a low application rate, and its compatibility with crop plants is sufficient for commercial use.

此目的及其他目的可利用式I所定義化合物及其農業上適用之鹽達成。This and other objects can be achieved using the compounds defined by Formula I and their agriculturally acceptable salts.

因此，本發明係有關以通式I哌化合物或式I哌化合物之農業上適用之鹽作為除草劑上之用途，亦即用於控制有害植物。Therefore, the present invention relates to the formula I Compound or formula I The agriculturally applicable salt of the compound is used as a herbicide for controlling harmful plants.

本發明亦有關一種組合物，其包含除草有效量之至少一種式I哌化合物或I之農業上適用之鹽與調配作物保護劑時常用之輔助物質。The invention also relates to a composition comprising a herbicidally effective amount of at least one of the formula I An agriculturally acceptable salt of a compound or I and an auxiliary substance commonly used in the formulation of a crop protection agent.

此外，本發明係有關一種控制不要之植物生長之方法，其包括由除草有效量之至少一種式I哌化合物或I之農業上適用之鹽作用在植物、其種子與/或其棲息地上。Furthermore, the present invention relates to a method for controlling unwanted plant growth comprising at least one herbicidal effective amount of the formula I The agriculturally suitable salt of the compound or I acts on the plant, its seeds and/or its habitat.

式I哌化合物為新穎化合物，亦形成本發明主題之一部份，－但不包括式I中A1 為苯基與A2 為4－咪唑基或A1 為4－咪唑基與A2 為苯基之化合物，－亦不包括式I中R1 為氫與R2 為甲基，R3 、R4 、R5 與R6 為氫，基團A1 (Ra Rb Rc )為4－甲氧基苯基與基團(Rd Re Rf )為苯基之化合物，－亦不包括式I中A1 為苯基，R1 與R2 為甲基，R3 、R4 、R5 與R6 為氫，Ra 為附接在3－位置之苯甲基氧，Rb 與Rc 為氫，基團A2 (Rd Re Rf )為苯基或3－硝基苯基之化合物，－亦不包括式I中R1 為氫、乙醯基或異丙基氧羰基，R2 為氫或苯甲基，R3 、R4 、R5 與R6 為氫，基團A1 (Ra Rb Rc )為如下式基團之化合物 其中#表示附接帶有R3 之次甲基碳，基團A2 (Rd Re Rf )為3－甲基－4－甲氧基苯基。Formula I The compound is a novel compound which also forms part of the subject matter of the present invention - but does not include a formula in which A 1 is a phenyl group and A 2 is a 4-imidazolyl group or A 1 is a 4-imidazolyl group and A 2 is a phenyl group. The compound, - also excluding R in the formula I, wherein R 1 is hydrogen and R 2 is methyl, R 3 , R 4 , R 5 and R 6 are hydrogen, and the group A 1 (R a R b R c ) is 4-methyl. A compound having an oxyphenyl group and a group (R d R e R f ) which is a phenyl group, - does not include a formula wherein A 1 is a phenyl group, R 1 and R 2 are a methyl group, and R 3 , R 4 , R 5 and R 6 are hydrogen, R a is a benzyl oxygen attached at the 3-position, R b and R c are hydrogen, and the group A 2 (R d R e R f ) is a phenyl or 3-nitro group. The compound of phenyl, - does not include R 1 in formula I wherein R 1 is hydrogen, ethinyl or isopropyloxycarbonyl, R 2 is hydrogen or benzyl, and R 3 , R 4 , R 5 and R 6 are hydrogen, a group A 1 (R a R b R c ) is a compound of the formula Where # represents the attachment of a methine carbon with R 3 and the group A 2 (R d R e R f ) is 3-methyl-4-methoxyphenyl.

－亦不包括式I中R1 為異丙基氧羰基與R2 為苯甲基，R3 、R4 、R5 與R6 為氫，基團A1 (Ra Rb Rc )與A2 (Rd Re Rf )分別為3,4,5－三甲氧基苯基之化合物。- also excluding R in the formula I wherein R 1 is isopropyloxycarbonyl and R 2 is benzyl, R 3 , R 4 , R 5 and R 6 are hydrogen, and the group A 1 (R a R b R c ) A 2 (R d R e R f ) is a compound of 3,4,5-trimethoxyphenyl, respectively.

此外，本發明係有關製備式I化合物之方法及中間物。Furthermore, the invention relates to methods and intermediates for the preparation of compounds of formula I.

此外，本發明具體實施例可由請求項、說明書與實例中了解。咸了解，如上述特色及本發明主題之詳細說明不僅可應用於各特別指定實例之組合中，且可在不偏離本發明範圍下應用於其他組合。Furthermore, the specific embodiments of the present invention can be understood from the claims, the description and the examples. The above description and the detailed description of the subject matter of the present invention are applicable not only to the combinations of the specified embodiments but also to other combinations without departing from the scope of the invention.

依取代型態而定，式I化合物可能包括一個或多個對掌性中心，此時可能出現對映異構物或非對映異構物混合物。本發明提供純對映異構物或非對映異構物與其混合物。Depending on the type of substitution, the compound of formula I may include one or more pairs of palmitic centers, in which case enantiomeric or diastereomeric mixtures may occur. The present invention provides pure enantiomers or diastereomers and mixtures thereof.

式I化合物亦可呈其農業上適用之鹽型，鹽之性質通常不重要。合適鹽類通常為所含陽離子與陰離子不會負面影響化合物I除草作用之彼等陽離子之鹽類及彼等酸類之酸加成鹽類。The compounds of formula I may also be in the form of their agriculturally suitable salts, the nature of which is generally not critical. Suitable salts are generally the salts of the cations of the cations and anions which do not adversely affect the herbicidal action of the compound I and the acid addition salts of the same.

合適陽離子特定言之為鹼金屬離子，較佳為鋰、鈉或鉀，鹼土金屬離子，較佳為鈣或鎂，及過渡金屬離子，較佳為錳、銅、鋅或鐵。同樣要可使用銨作為陽離子，其中若需要時，1至4個氫原子可被C1 －C4 －烷基、羥基－C1 －C4 －烷基、C1 －C4 －烷氧基－C1 －C4 －烷基、羥基－C1 －C4 －烷氧基－C1 －C4 －烷基、苯基或苯甲基置換，較佳為銨、二甲基銨、二異丙基銨、四甲基銨、四丁基銨、2－(2－羥基乙－1－氧)乙－1－基銨、二(2－羥基乙－1－基)銨、三甲基苯甲基銨。亦可述及鏻離子、鋶離子，較佳為三(C1 －C4 －烷基)鋶離子與氧化鋶離子，較佳為三(C1 －C4 －烷基)氧化鋶離子。Suitable cations are specifically alkali metal ions, preferably lithium, sodium or potassium, alkaline earth metal ions, preferably calcium or magnesium, and transition metal ions, preferably manganese, copper, zinc or iron. It is likewise desirable to use ammonium as the cation, wherein if desired, 1 to 4 hydrogen atoms may be C 1 -C 4 -alkyl, hydroxy-C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy -C 1 -C 4 -alkyl, hydroxy-C 1 -C 4 -alkoxy-C 1 -C 4 -alkyl, phenyl or benzyl substituted, preferably ammonium, dimethyl ammonium, Isopropylammonium, tetramethylammonium, tetrabutylammonium, 2-(2-hydroxyethyl-1-oxo)eth-1-ylammonium, bis(2-hydroxyethyl-1-yl)ammonium, trimethyl Benzyl ammonium. Further, a cerium ion or a cerium ion may be mentioned, preferably a tri(C 1 -C 4 -alkyl)phosphonium ion and a cerium oxide ion, preferably a tri(C 1 -C 4 -alkyl) cerium oxide ion.

適用之酸加成鹽之陰離子主要為氯離子、溴離子、氟離子、硫酸氫根、硫酸根、磷酸二氫根、磷酸氫根、硝酸根、碳酸氫根、碳酸根、六氟矽酸根、六氟磷酸根、苯甲酸根，與C1 －C4 －烷酸類之陰離子，較佳為甲酸根、乙酸根、丙酸根與丁酸根。Suitable anions of acid addition salts are mainly chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, nitrate, bicarbonate, carbonate, hexafluoroantimonate, An anion of hexafluorophosphate, benzoate, and a C 1 -C 4 -alkanoic acid, preferably formate, acetate, propionate and butyrate.

根據本發明化合物之取代基所述及有機部份基團係各所指定族群成員之個別基團總稱。所有烴鏈，如：烷基、鹵烷基，及下列基團之烷基部份基團：氰基烷基、烷氧基、鹵烷氧基、烷基硫、鹵烷基硫、烷基亞磺醯基、鹵烷基亞磺醯基、烷基磺醯基、鹵烷基磺醯基、N－烷基胺基磺醯基、N,N－二烷基胺基磺醯基、二烷基胺基、N－烷基磺醯基胺基、N－鹵烷基磺醯基胺基、N－烷基－N－烷基磺醯基胺基、N－烷基－N－鹵烷基磺醯基胺基、烷基羰基、鹵烷基羰基、烷氧基羰基、鹵烷氧基羰基、烷基羰基氧、烷基胺基羰基、二烷基胺基羰基、二烷基胺基硫羰基、烷氧基烷基、二烷氧基烷基、烷基硫烷基、二烷基胺基烷基、二烷基聯胺基烷基、烷基亞胺基氧烷基、烷基羰基烷基、烷氧基亞胺基烷基、N－(烷基胺基)亞胺基烷基、N－(二烷基胺基)亞胺基烷基、烷氧基羰基烷基、二烷基胺基羰基烷基、苯基烯基羰基、雜環基烯基羰基、N－烷氧基－N－烷基胺基羰基、N－烷基－N－苯基胺基羰基、N－烷基－N－雜環基胺基羰基、苯基烷基、雜環基烷基、苯基羰基烷基、雜環基羰基烷基、二烷基胺基烷氧基羰基、烷氧基烷氧基羰基、烯基羰基、烯基氧羰基、烯基胺基羰基、N－烯基－N－烷基胺基羰基、N－烯基－N－烷氧基胺基羰基、炔基羰基、炔基氧羰基、炔基胺基羰基、N－炔基－N－烷基胺基羰基、N－炔基－N－烷氧基胺基羰基、烯基、炔基、鹵烯基、鹵炔基與烷氧基烷氧基部份基團可為直鏈或分支。字首Cn －Cm －指烴部份基團之各碳原子數。除非本文中另有說明，否則鹵化取代基最好帶有1至5個相同或相異鹵原子，特定言之氟原子或氯原子。The individual groups of the members of the specified group according to the substituents of the compounds of the present invention and the organic moiety groups are collectively referred to. All hydrocarbon chains, such as alkyl, haloalkyl, and alkyl moiety of the following groups: cyanoalkyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkyl Sulfosyl, haloalkylsulfinyl, alkylsulfonyl, haloalkylsulfonyl, N-alkylaminosulfonyl, N,N-dialkylaminosulfonyl, two Alkylamino, N-alkylsulfonylamino, N-haloalkylsulfonylamino, N-alkyl-N-alkylsulfonylamino, N-alkyl-N-halane Sulfosylamino, alkylcarbonyl, haloalkylcarbonyl, alkoxycarbonyl, haloalkoxycarbonyl, alkylcarbonyloxy, alkylaminocarbonyl, dialkylaminocarbonyl, dialkylamino Thiocarbonyl, alkoxyalkyl, dialkoxyalkyl, alkylsulfanyl, dialkylaminoalkyl, dialkylbiminoalkyl, alkyliminooxyalkyl, alkyl Carbonylalkyl, alkoxyiminoalkyl, N-(alkylamino)iminoalkyl, N-(dialkylamino)iminoalkyl, alkoxycarbonylalkyl, two Alkylaminocarbonylalkyl, phenylalkenylcarbonyl, heterocyclylalkenylcarbonyl, N-alkoxy-N-alkane Aminocarbonyl, N-alkyl-N-phenylaminocarbonyl, N-alkyl-N-heterocyclylaminocarbonyl, phenylalkyl, heterocyclylalkyl, phenylcarbonylalkyl, heterocycle Alkylcarbonylalkyl, dialkylaminoalkoxycarbonyl, alkoxyalkoxycarbonyl, alkenylcarbonyl, alkenyloxycarbonyl, alkenylaminocarbonyl, N-alkenyl-N-alkylaminocarbonyl , N-alkenyl-N-alkoxyaminocarbonyl, alkynylcarbonyl, alkynyloxycarbonyl, alkynylaminocarbonyl, N-alkynyl-N-alkylaminocarbonyl, N-alkynyl-N- The alkoxyaminocarbonyl, alkenyl, alkynyl, haloalkenyl, haloalkynyl and alkoxyalkoxy moiety may be straight or branched. The prefix C n -C m - refers to the number of carbon atoms of the hydrocarbon moiety. Unless otherwise stated herein, the halogenated substituent preferably has from 1 to 5 identical or distinct halogen atoms, specifically a fluorine atom or a chlorine atom.

鹵素一詞分別指氟、氯、溴或碘。The term halogen means fluorine, chlorine, bromine or iodine, respectively.

其他定義之實例為：烷基，及例如：烷氧基、烷基硫、烷基亞磺醯基與烷基磺醯基、烷基羰基、烷基胺基、烷基矽烷基、苯基烷基、苯基磺醯基烷基、雜環基烷基中之烷基部份基團：具有一個或多個碳原子，例如：1至2個，1至4個或1至6個碳原子之飽和直鏈或分支烴，例如：C1 －C6 －烷基，如：甲基、乙基、丙基、1－甲基乙基、丁基、1－甲基丙基、2－甲基丙基、1,1－二甲基乙基、戊基、1－甲基丁基、2－甲基丁基、3－甲基丁基、2,2－二甲基丙基、1－乙基丙基、己基、1,1－二甲基丙基、1,2－二甲基丙基、1－甲基戊基、2－甲基戊基、3－甲基戊基、4－甲基戊基、1,1－二甲基丁基、1,2－二甲基丁基、1,3－二甲基丁基、2,2－二甲基丁基、2,3－二甲基丁基、3,3－二甲基丁基、1－乙基丁基、2－乙基丁基、1,1,2－三甲基丙基、1,2,2－三甲基丙基、1－乙基－1－甲基丙基、1－乙基－2－甲基丙基。根據本發明一項具體實施例中，烷基指小型烷基，如：C1 －C4 －烷基。根據本發明另一項具體實施例中，烷基指相當大烷基，如：C5 －C6 －烷基。Examples of other definitions are: alkyl groups, and for example: alkoxy groups, alkyl sulfurs, alkyl sulfinylene groups and alkyl sulfonyl groups, alkylcarbonyl groups, alkyl amine groups, alkyl decyl groups, phenyl groups Alkyl moiety in a phenylsulfonylalkyl group or a heterocyclylalkyl group having one or more carbon atoms, for example: 1 to 2, 1 to 4 or 1 to 6 carbon atoms a saturated linear or branched hydrocarbon such as a C 1 -C 6 -alkyl group such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methyl Propyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1- Ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4- Methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-di Methyl butyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethyl Propyl, 1-ethyl-1- Propyl, 1-ethyl-2-methylpropyl. According to a particular embodiment of the invention, alkyl refers to a small alkyl group such as a C 1 -C 4 -alkyl group. According to another particular embodiment of the present invention, alkyl refers to a large group, such as: C 5 -C 6 - alkyl.

鹵烷基：其氫原子經鹵原子(如：氟、氯、溴與/或碘)部份或完全取代之如上述烷基，例如：氯甲基、二氯甲基、三氯甲基、氟甲基、二氟甲基、三氟甲基、氯氟甲基、二氯氟甲基、氯二氟甲基、2－氟乙基、2－氯乙基、2－溴乙基、2－碘乙基、2,2－二氟乙基、2,2,2－三氟乙基、2－氯－2－氟乙基、2－氯－2,2－二氟乙基、2,2－二氯－2－氟乙基、2,2,2－三氯乙基、五氟乙基、2－氟丙基、3－氟丙基、2,2－二氟丙基、2,3－二氟丙基、2－氯丙基、3－氯丙基、2,3－二氯丙基、2－溴丙基、3－溴丙基、3,3,3－三氟丙基、3,3,3－三氯丙基、2,2,3,3,3－五氟丙基、七氟丙基、1－(氟甲基)－2－氟乙基、1－(氯甲基)－2－氯乙基、1－(溴甲基)－2－溴乙基、4－氟丁基、4－氯丁基、4－溴丁基與九氟丁基。Haloalkyl group: a hydrogen atom thereof partially or completely substituted with a halogen atom (e.g., fluorine, chlorine, bromine, and/or iodine) such as the above alkyl group, for example, chloromethyl, dichloromethyl, trichloromethyl, Fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2 - iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2, 2-Dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2, 3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl ,3,3,3-trichloropropyl, 2,2,3,3,3-pentafluoropropyl, heptafluoropropyl, 1-(fluoromethyl)-2-fluoroethyl, 1-(chloro Methyl)-2-chloroethyl, 1-(bromomethyl)-2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl and nonafluorobutyl.

環烷基與例如：環烷氧基或環烷基羰基中環烷基部份基團：具有三個或多個碳原子(例如：3至6個碳環組員)之單環飽和烴基，如：環丙基、環丁基、環戊基與環己基。a cycloalkyl group and, for example, a cycloalkyloxy group or a cycloalkylcarbonyl group: a monocyclic saturated hydrocarbon group having three or more carbon atoms (for example, 3 to 6 carbon ring members), such as: Cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.

烯基與例如：苯基－(C2 －C6 )－烯基或烯基胺基中之烯基部份基團：具有兩個或多個碳原子，例如：2至4個，2Alkenyl group with, for example, an alkenyl moiety in a phenyl-(C 2 -C 6 )-alkenyl or alkenylamino group: having two or more carbon atoms, for example: 2 to 4, 2

至6個或3至6個碳原子，與任何位置上之一個雙鍵之直鏈或分支烴基，例如：C2 －C6 －烯基，如：乙烯基、1－丙烯基、2－丙烯基、1－甲基乙烯基、1－丁烯基、2－丁烯基、3－丁烯基、1－甲基－1－丙烯基、2－甲基－1－丙烯基、1－甲基－2－丙烯基、2－甲基－2－丙烯基、1－戊烯基、2－戊烯基、3－戊烯基、4－戊烯基、1－甲基－1－丁烯基、2－甲基－1－丁烯基、3－甲基－1－丁烯基、1－甲基－2－丁烯基、2－甲基－2－丁烯基、3－甲基－2－丁烯基、1－甲基－3－丁烯基、2－甲基－3－丁烯基、3－甲基－3－丁烯基、1,1－二甲基－2－丙烯基、1,2－二甲基－1－丙烯基、1,2－二甲基－2－丙烯基、1－乙基－1－丙烯基、1－乙基－2－丙烯基、1－己烯基、2－己烯基、3－己烯基、4－己烯基、5－己烯基、1－甲基－1－戊烯基、2－甲基－1－戊烯基、3－甲基－1－戊烯基、4－甲基－1－戊烯基、1－甲基－2－戊烯基、2－甲基－2－戊烯基、3－甲基－2－戊烯基、4－甲基－2－戊烯基、1－甲基－3－戊烯基、2－甲基－3－戊烯基、3－甲基－3－戊烯基、4－甲基－3－戊烯基、1－甲基－4－戊烯基、2－甲基－4－戊烯基、3－甲基－4－戊烯基、4－甲基－4－戊烯基、1,1－二甲基－2－丁烯基、1,1－二甲基－3－丁烯基、1,2－二甲基－1－丁烯基、1,2－二甲基－2－丁烯基、1,2－二甲基－3－丁烯基、1,3－二甲基－1－丁烯基、1,3－二甲基－2－丁烯基、1,3－二甲基－3－丁烯基、2,2－二甲基－3－丁烯基、2,3－二甲基－1－丁烯基、2,3－二甲基－2－丁烯基、2,3－二甲基－3－丁烯基、3,3－二甲基－1－丁烯基、3,3－二甲基－2－丁烯基、1－乙基－1－丁烯基、1－乙基－2－丁烯基、1－乙基－3－丁烯基、2－乙基－1－丁烯基、2－乙基－2－丁烯基、2－乙基－3－丁烯基、1,1,2－三甲基－2－丙烯基、1－乙基－1－甲基－2－丙烯基、1－乙基－2－甲基－1－丙烯基、1－乙基－2－甲基－2－丙烯基。a linear or branched hydrocarbon group of 6 or 3 to 6 carbon atoms, and a double bond at any position, for example, a C 2 -C 6 -alkenyl group such as a vinyl group, a 1-propenyl group, or a 2-propene group. Base, 1-methylvinyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl 2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butene Base, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl 2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2- Propylene, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1 -hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl 3-methyl-1- Alkenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl 2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentene , 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-pentenyl, 4-methyl-4-pentenyl, 1,1- Dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1,2-dimethyl-2-butene 1,1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl 3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-Dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butene Alkenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butene Base, 2-ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2- Methyl-1-propenyl, 1-ethyl-2-methyl-2-propenyl.

根據本發明一項具體實施例中，係使用如：C2 －C6 －烯基之烯基。根據本發明另一項具體實施例中，係使用如：C3 －C6 －烯基之烯基。According to a particular embodiment of the invention, an alkenyl group such as a C 2 -C 6 -alkenyl group is used. According to another embodiment of the invention, an alkenyl group such as a C 3 -C 6 -alkenyl group is used.

環烯基與環烯基部份基團：具有三個或多個碳原子，例如：3至6個，較佳為5至6個碳環組員之單環狀單不飽和烴基，如：環戊烯－1－基、環戊烯－3－基、環己烯－1－基、環己烯－3－基、環己烯－4－基。a cycloalkenyl group and a cycloalkenyl moiety: a monocyclic monounsaturated hydrocarbon group having three or more carbon atoms, for example, 3 to 6, preferably 5 to 6 carbon ring members, such as a ring Penten-1-yl, cyclopenten-3-yl, cyclohexen-1-yl, cyclohexen-3-yl, cyclohexen-4-yl.

炔基與例如：[三－(C1 －C6 )－烷基矽烷基－(C2 －C6 )－炔基或炔基胺基中炔基部份基團：具有兩個或多個碳原子，例如：2至4個，2至6個或3至6個碳原子及任何位置上但不可相鄰之1或2個參鍵之直鏈或分支烴，例如：C2 －C6 －炔基，如：乙炔基、1－丙炔基、2－丙炔基、1－丁炔基、2－丁炔基、3－丁炔基、1－甲基－2－丙炔基、1－戊炔基、2－戊炔基、3－戊炔基、4－戊炔基、1－甲基－2－丁炔基、1－甲基－3－丁炔基、2－甲基－3－丁炔基、3－甲基－1－丁炔基、1,1－二甲基－2－丙炔基、1－乙基－2－丙炔基、1－己炔基、2－己炔基、3－己炔基、4－己炔基、5－己炔基、1－甲基－2－戊炔基、1－甲基－3－戊炔基、1－甲基－4－戊炔基、2－甲基－3－戊炔基、2－甲基－4－戊炔基、3－甲基－1－戊炔基、3－甲基－4－戊炔基、4－甲基－1－戊炔基、4－甲基－2－戊炔基、1,1－二甲基－2－丁炔基、1,1－二甲基－3－丁炔基、1,2－二甲基－3－丁炔基、2,2－二甲基－3－丁炔基、3,3－二甲基－1－丁炔基、1－乙基－2－丁炔基、1－乙基－3－丁炔基、2－乙基－3－丁炔基、1－乙基－1－甲基－2－丙炔基。Alkynyl with, for example: [tri-(C 1 -C 6 )-alkyldecyl-(C 2 -C 6 )-alkynyl or alkynylamino) alkynyl moiety: having two or more a carbon atom, for example, 2 to 4, 2 to 6 or 3 to 6 carbon atoms, and a straight or branched hydrocarbon at any position but not adjacent to one or two of the bonds, for example, C 2 -C 6 Alkynyl, such as: ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl 3-butynyl, 3-methyl-1-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2 -hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl- 4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4-pentynyl, 4-methyl-1-pentynyl, 4-methyl 2-pentynyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2, 2-dimethyl-3-butynyl, 3,3-dimethyl-1-butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2- Ethyl-3-butynyl, 1-ethyl-1-methyl-2-propynyl.

環炔基與環炔基部份基團：具有三個或多個碳原子，例如：3至6個，較佳為5至6個碳環組員與一個參鍵之單環烴，如：環己炔－1－基、環己炔－3－基、環己炔－4－基。a cycloalkynyl group and a cycloalkynyl moiety: having three or more carbon atoms, for example, 3 to 6, preferably 5 to 6 carbon ring members and a single bond, such as a ring. Hexyn-1-yl, cyclohexyn-3-yl, cyclohexyn-4-yl.

C4 －C10 －烷二烯基：具有4個或多個碳原子與任何位置上但不可相鄰之2個雙鍵，例如：4至10個碳原子與任何位置上但不可相鄰之2個雙鍵之雙不飽和直鏈或分支烴，例如：1,3－丁二烯基丁二烯基、1－甲基－1,3－丁二烯基、2－甲基－1,3－丁二烯基、戊－1,3－二烯－1－基、己－1,4－二烯－1－基、己－1,4－二烯－3－基、己－1,4－二烯－6－基、己－1,5－二烯－1－基、己－1,5－二烯－3－基、己－1,5－二烯－4－基、庚－1,4－二烯－1－基、庚－1,4－二烯－3－基、庚－1,4－二烯－6－基、庚－1,4－二烯－7－基、庚－1,5－二烯－1－基、庚－1,5－二烯－3－基、庚－1,5－二烯－4－基、庚－1,5－二烯－7－基、庚－1,6－二烯－1－基、庚－1,6－二烯－3－基、庚－1,6－二烯－4－基、庚－1,6－二烯－5－基、庚－1,6－二烯－2－基、辛－1,4－二烯－1－基、辛－1,4－二烯－2－基、辛－1,4－二烯－3－基、辛－1,4－二烯－6－基、辛－1,4－二烯－7－基、辛－1,5－二烯－1－基、辛－1,5－二烯－3－基、辛－1,5－二烯－4－基、辛－1,5－二烯－7－基、辛－1,6－二烯－1－基、辛－1,6－二烯－3－基、辛－1,6－二烯－4－基、辛－1,6－二烯－5－基、辛－1,6－二烯－2－基、癸－1,－4－二烯基、癸－1,5－二烯基、癸－1,6－二烯基、癸－1,7－二烯基、癸－1,8－二烯基、癸－2,5－二烯基、癸－2,6－二烯基、癸－2,7－二烯基、癸－2,8－二烯基。C 4 -C 10 -aldienyl: 2 double bonds having 4 or more carbon atoms and any position but not adjacent, for example: 4 to 10 carbon atoms and not adjacent to any position 2 double-bonded diunsaturated linear or branched hydrocarbons, for example: 1,3-butadienylbutadienyl, 1-methyl-1,3-butadienyl, 2-methyl-1, 3-butadienyl, pentane-1,3-dien-1-yl, hexa-1,4-dien-1-yl, hexa-1,4-dien-3-yl, hex-1, 4-dien-6-yl, hex-1,5-dien-1-yl, hex-1,5-dien-3-yl, hex-1,5-dien-4-yl, g- 1,4-dien-1-yl, heptane-1,4-dien-3-yl, heptane-1,4-diene-6-yl, heptane-1,4-diene-7-yl, Gh-1,5-dien-1-yl, g-1,5-dien-3-yl, g-1,5-dien-4-yl, g-1,5-diene-7- Base, hept-1,6-dien-1-yl, hept-1,6-dien-3-yl, hept-1,6-dien-4-yl, hept-1,6-diene- 5-yl, hept-1,6-dien-2-yl, octane-1,4-dien-1-yl, octane-1,4-diene-2 Base, octane-1,4-dien-3-yl, octane-1,4-diene-6-yl, octyl-1,4-diene-7-yl, octane-1,5-diene- 1-yl, oct-1,5-dien-3-yl, oct-1,5-dien-4-yl, oct-1,5-dien-7-yl, oct-1,6-di En-1-yl, oct-1,6-dien-3-yl, oct-1,6-dien-4-yl, oct-1,6-dien-5-yl, oct-1,6 -dien-2-yl, indol-1,-4-dienyl, indol-1,5-dienyl, indol-1,6-dienyl, indole-1,7-dienyl, anthracene -1,8-dienyl, indole-2,5-dienyl, indole-2,6-dienyl, indole-2,7-dienyl, indole-2,8-dienyl.

烷氧基或例如：苯基烷氧基、烷氧基胺基、烷氧基羰基中之烷氧基部份基團：利用氧原子附接之如上述定義烷基：例如：甲氧基、乙氧基、正丙氧基、1－甲基乙氧基、丁氧基、1－甲基丙氧基、2－甲基丙氧基或1,1－二甲基乙氧基、戊氧基、1－甲基丁氧基、2－甲基丁氧基、3－甲基丁氧基、1,1－二甲基丙氧基、1,2－二甲基丙氧基、2,2－二甲基丙氧基、1－乙基丙氧基、己氧基、1－甲基戊氧基、2－甲基戊氧基、3－甲基戊氧基、4－甲基戊氧基、1,1－二甲基丁氧基、1,2－二甲基丁氧基、1,3－二甲基丁氧基、2,2－二甲基丁氧基、2,3－二甲基丁氧基、3,3－二甲基丁氧基、1－乙基丁氧基、2－乙基丁氧基、1,1,2－三甲基丙氧基、1,2,2－三甲基丙氧基、1－乙基－1－甲基丙氧基或1－乙基－2－甲基丙氧基。An alkoxy group or an alkoxy moiety in a phenylalkoxy group, an alkoxyamino group or an alkoxycarbonyl group: an alkyl group as defined above, which is attached by an oxygen atom: for example, a methoxy group, Ethoxy, n-propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy or 1,1-dimethylethoxy, pentoxide , 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 1,1-dimethylpropoxy, 1,2-dimethylpropoxy, 2, 2-Dimethylpropoxy, 1-ethylpropoxy, hexyloxy, 1-methylpentyloxy, 2-methylpentyloxy, 3-methylpentyloxy, 4-methylpentyl Oxyl, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1,3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3 - dimethylbutoxy, 3,3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1,1,2-trimethylpropoxy, 1, 2,2-Trimethylpropoxy, 1-ethyl-1-methylpropoxy or 1-ethyl-2-methylpropoxy.

根據本發明一項具體實施例中，使用小型烷氧基如：C1 －C4 －烷氧基。根據本發明另一項具體實施例中，使用相當大型烷氧基，如：C5 －C6 －烷氧基。According to a particular embodiment of the invention, a small alkoxy group such as a C 1 -C 4 -alkoxy group is used. According to another embodiment of the invention, a relatively large alkoxy group, such as a C 5 -C 6 -alkoxy group, is used.

烯基氧：利用氧原子附接之如上述定義烯基：例如：C3 －C6 －烯基氧,如：1－丙烯基氧、2－丙烯基氧、1－甲基乙烯基氧、1－丁烯基氧、2－丁烯基氧、3－丁烯基氧、1－甲基－1－丙烯基氧、2－甲基－1－丙烯基氧、1－甲基－2－丙烯基氧、2－甲基－2－丙烯基氧、1－戊烯基氧、2－戊烯基氧、3－戊烯基氧、4－戊烯基氧、1－甲基－1－丁烯基氧、2－甲基－1－丁烯基氧、3－甲基－1－丁烯基氧、1－甲基－2－丁烯基氧、2－甲基－2－丁烯基氧、3－甲基－2－丁烯基氧、1－甲基－3－丁烯基氧、2－甲基－3－丁烯基氧、3－甲基－3－丁烯基氧、1,1－二甲基－2－丙烯基氧、1,2－二甲基－1－丙烯基氧、1,2－二甲基－2－丙烯基氧、1－乙基－1－丙烯基氧、1－乙基－2－丙烯基氧、1－己烯基氧、2－己烯基氧、3－己烯基氧、4－己烯基氧、5－己烯基氧、1－甲基－1－戊烯基氧、2－甲基－1－戊烯基氧、3－甲基－1－戊烯基氧、4－甲基－1－戊烯基氧、1－甲基－2－戊烯基氧、2－甲基－2－戊烯基氧、3－甲基－2－戊烯基氧、4－甲基－2－戊烯基氧、1－甲基－3－戊烯基氧、2－甲基－3－戊烯基氧、3－甲基－3－戊烯基氧、4－甲基－3－戊烯基氧、1－甲基－4－戊烯基氧、2－甲基－4－戊烯基氧、3－甲基－4－戊烯基氧、4－甲基－4－戊烯基氧、1,1－二甲基－2－丁烯基氧、1,1－二甲基－3－丁烯基氧、1,2－二甲基－1－丁烯基氧、1,2－二甲基－2－丁烯基氧、1,2－二甲基－3－丁烯基氧、1,3－二甲基－1－丁烯基氧、1,3－二甲基－2－丁烯基氧、1,3－二甲基－3－丁烯基氧、2,2－二甲基－3－丁烯基氧、2,3－二甲基－1－丁烯基氧、2,3－二甲基－2－丁烯基氧、2,3－二甲基－3－丁烯基氧、3,3－二甲基－1－丁烯基氧、3,3－二甲基－2－丁烯基氧、1－乙基－1－丁烯基氧、1－乙基－2－丁烯基氧、1－乙基－3－丁烯基氧、2－乙基－1－丁烯基氧、2－乙基－2－丁烯基氧、2－乙基－3－丁烯基氧、1,1,2－三甲基－2－丙烯基氧、1－乙基－1－甲基－2－丙烯基氧、1－乙基－2－甲基－1－丙烯基氧與1－乙基－2－甲基－2－丙烯基氧。根據本發明一項具體實施例中，使用小型烯基氧基團，如：C3 －C4 －烯基氧。根據本發明另一項具體實施例中，使用相當大型烯基氧基團，如：C5 －C6 －烯基氧。Alkenyloxy: an alkenyl group as defined above, attached by an oxygen atom: for example: C 3 -C 6 -alkenyloxy, such as 1-propenyloxy, 2-propenyloxy, 1-methylvinyloxy, 1-butenyloxy, 2-butenyloxy, 3-butenyloxy, 1-methyl-1-propenyloxy, 2-methyl-1-propenyloxy, 1-methyl-2- Propenyloxy, 2-methyl-2-propenyloxy, 1-pentenyloxy, 2-pentenyloxy, 3-pentenyloxy, 4-pentenyloxy, 1-methyl-1- Butenyloxy, 2-methyl-1-butenyloxy, 3-methyl-1-butenyloxy, 1-methyl-2-butenyloxy, 2-methyl-2-butene Base oxygen, 3-methyl-2-butenyloxy, 1-methyl-3-butenyloxy, 2-methyl-3-butenyloxy, 3-methyl-3-butenyloxy 1,1-dimethyl-2-propenyloxy, 1,2-dimethyl-1-propenyloxy, 1,2-dimethyl-2-propenyloxy, 1-ethyl-1- Propenyloxy, 1-ethyl-2-propenyloxy, 1-hexenyloxy, 2-hexenyloxy, 3-hexenyloxy, 4-hexenyloxy, 5-hexenyloxy, 1-methyl-1- Alkenyloxy, 2-methyl-1-pentenyloxy, 3-methyl-1-pentenyloxy, 4-methyl-1-pentenyloxy, 1-methyl-2-pentenyl Oxygen, 2-methyl-2-pentenyloxy, 3-methyl-2-pentenyloxy, 4-methyl-2-pentenyloxy, 1-methyl-3-pentenyloxy, 2-methyl-3-pentenyloxy, 3-methyl-3-pentenyloxy, 4-methyl-3-pentenyloxy, 1-methyl-4-pentenyloxy, 2- Methyl-4-pentenyloxy, 3-methyl-4-pentenyloxy, 4-methyl-4-pentenyloxy, 1,1-dimethyl-2-butenyloxy, 1 ,1-dimethyl-3-butenyloxy, 1,2-dimethyl-1-butenyloxy, 1,2-dimethyl-2-butenyloxy, 1,2-dimethyl 3-butenyloxy, 1,3-dimethyl-1-butenyloxy, 1,3-dimethyl-2-butenyloxy, 1,3-dimethyl-3-butyl Alkenyloxy, 2,2-dimethyl-3-butenyloxy, 2,3-dimethyl-1-butenyloxy, 2,3-dimethyl-2-butenyloxy, 2 ,3-dimethyl-3-butenyloxy, 3,3-dimethyl-1-butenyloxy, 3,3-dimethyl-2-butene Base oxygen, 1-ethyl-1-butenyloxy, 1-ethyl-2-butenyloxy, 1-ethyl-3-butenyloxy, 2-ethyl-1-butenyloxy , 2-ethyl-2-butenyloxy, 2-ethyl-3-butenyloxy, 1,1,2-trimethyl-2-propenyloxy, 1-ethyl-1-methyl 2-propenyloxy, 1-ethyl-2-methyl-1-propenyloxy and 1-ethyl-2-methyl-2-propenyloxy. According to an embodiment of the present invention, a small alkenyloxy groups such as: C 3 -C 4 - alkenyl oxygen. According to another embodiment of the invention, a relatively large alkenyloxy group, such as a C 5 -C 6 -alkenyloxy group, is used.

炔基氧：利用氧原子附接如上述定義之炔基，例如：C3 －C6 －炔基氧，如：2－丙炔基氧、2－丁炔基氧、3－丁炔基氧、1－甲基－2－丙炔基氧、2－戊炔基氧、3－戊炔基氧、4－戊炔基氧、1－甲基－2－丁炔基氧、1－甲基－3－丁炔基氧、2－甲基－3－丁炔基氧、1－乙基－2－丙炔基氧、2－己炔基氧、3－己炔基氧、4－己炔基氧、5－己炔基氧、1－甲基－2－戊炔基氧、1－甲基－3－戊炔基氧。根據本發明一項具體實施例中，使用小型炔基氧基團，如：C3 －C4 －炔基氧。根據本發明另一項具體實施例中，使用相當大型炔基氧基團，如：C5 －C6 －炔基氧。Alkynyloxy: an alkynyl group as defined above is attached using an oxygen atom, for example: C 3 -C 6 -alkynyloxy, such as 2-propynyloxy, 2-butynyloxy, 3-butynyloxy , 1-methyl-2-propynyloxy, 2-pentynyloxy, 3-pentynyloxy, 4-pentynyloxy, 1-methyl-2-butynyloxy, 1-methyl 3-butynyloxy, 2-methyl-3-butynyloxy, 1-ethyl-2-propynyloxy, 2-hexynyloxy, 3-hexynyloxy, 4-hexyne Oxygen, 5-hexynyloxy, 1-methyl-2-pentynyloxy, 1-methyl-3-pentynyloxy. According to a particular embodiment of the present invention, the use of small alkynyloxy groups such as: C 3 -C 4 - alkynyl oxygen. According to another embodiment of the invention, a relatively large alkynyloxy group such as a C 5 -C 6 -alkynyloxy group is used.

烷基硫：利用硫附接之如上述定義之烷基。Alkyl Sulfide: An alkyl group as defined above, attached by sulfur.

烷基亞磺醯基：利用SO基團附接之如上述定義之烷基。Alkylsulfinyl group: an alkyl group as defined above attached using an SO group.

烷基磺醯基：利用S(O)2 基團附接之如上述定義之烷基。Alkylsulfonyl: an alkyl group as defined above attached using a S(O) 2 group.

烷基羰基：利用(C＝O)基團附接之如上述定義之烷基。例如：甲基羰基、乙基羰基、丙基羰基、1－甲基乙基羰基、丁基羰基、1－甲基丙基羰基、2－甲基丙基羰基或1,1－二甲基乙基羰基、戊基羰基、1－甲基丁基羰基、2－甲基丁基羰基、3－甲基丁基羰基、2,2－二甲基丙基羰基、1－乙基丙基羰基、己基羰基、1,1－二甲基丙基羰基、1,2－二甲基丙基羰基、1－甲基戊基羰基、2－甲基戊基羰基、3－甲基戊基羰基、4－甲基戊基羰基、1,1－二甲基丁基羰基、1,2－二甲基丁基羰基、1,3－二甲基丁基羰基、2,2,－二甲基丁基羰基、2,3－二甲基丁基羰基、3,3－二甲基丁基羰基、1－乙基丁基羰基、2－乙基丁基羰基、1,1,2－三甲基丙基羰基、1,2,2－三甲基丙基羰基、1－乙基－1－甲基丙基羰基或1－乙基－2－甲基丙基羰基。Alkylcarbonyl: an alkyl group as defined above attached using a (C=O) group. For example: methylcarbonyl, ethylcarbonyl, propylcarbonyl, 1-methylethylcarbonyl, butylcarbonyl, 1-methylpropylcarbonyl, 2-methylpropylcarbonyl or 1,1-dimethylethyl Carbocarbonyl, pentylcarbonyl, 1-methylbutylcarbonyl, 2-methylbutylcarbonyl, 3-methylbutylcarbonyl, 2,2-dimethylpropylcarbonyl, 1-ethylpropylcarbonyl, Hexylcarbonyl, 1,1-dimethylpropylcarbonyl, 1,2-dimethylpropylcarbonyl, 1-methylpentylcarbonyl, 2-methylpentylcarbonyl, 3-methylpentylcarbonyl, 4 -methylpentylcarbonyl, 1,1-dimethylbutylcarbonyl, 1,2-dimethylbutylcarbonyl, 1,3-dimethylbutylcarbonyl, 2,2,-dimethylbutyl Carbonyl, 2,3-dimethylbutylcarbonyl, 3,3-dimethylbutylcarbonyl, 1-ethylbutylcarbonyl, 2-ethylbutylcarbonyl, 1,1,2-trimethylpropane Alkylcarbonyl, 1,2,2-trimethylpropylcarbonyl, 1-ethyl-1-methylpropylcarbonyl or 1-ethyl-2-methylpropylcarbonyl.

烯基羰基：利用(C＝O)基團附接之如上述定義之烯基，例如：1－乙烯基羰基。Alkenylcarbonyl: an alkenyl group as defined above, appended with a (C=O) group, for example: 1-vinylcarbonyl.

炔基羰基：利用(C＝O)基團附接之如上述定義之烷基，例如：1－丙炔基羰基。Alkynylcarbonyl: an alkyl group as defined above attached by a (C=O) group, for example: 1-propynylcarbonyl.

雜環基：具有三個或多個，例如：3至10個環原子之單環－或雙環飽和、部份不飽和或芳香系雜環，例如：包含1至4個相同或相異之選自氧、硫或氮所組成群中雜原子且可利用碳或氮附接之單環狀3－、4－、5－、6－或7－員雜環，例如：利用碳附接3－或4－員飽和或不飽和環，如：2－環氧乙烷基、2－環氧丙烷基、3－環氧丙烷基、2－吖基、3－硫雜環丁烷基、1－吖呾基、2－吖呾基。Heterocyclic group: a monocyclic or bicyclic saturated, partially unsaturated or aromatic heterocyclic ring having three or more, for example, 3 to 10 ring atoms, for example: containing 1 to 4 identical or different choices a monocyclic 3-, 4-, 5-, 6- or 7-membered heterocyclic ring attached to a hetero atom in a group consisting of oxygen, sulfur or nitrogen and which may be attached by carbon or nitrogen, for example: carbon-attached 3- Or a 4-membered saturated or unsaturated ring, such as: 2-oxiranyl, 2-epoxypropane, 3-epoxypropane, 2-hydrazine Base, 3-thietyl, 1-indenyl, 2-indenyl.

利用碳附接之5－員飽和環，如四氫呋喃－2－基、四氫呋喃－3－基、四氫噻吩－2－基、四氫噻吩－3－基、四氫吡咯－2－基、四氫吡咯－3－基、四氫吡唑－3－基、四氫吡唑－4－基、四氫異唑－3－基、四氫異唑－4－基、四氫異唑－5－基、1,2－噻茂烷－3－基、1,2－噻茂烷－4－基、1,2－噻茂烷－5－基、四氫異噻唑－3－基、四氫異噻唑－4－基、四氫異噻唑－5－基、1,2－二噻茂烷－3－基、1,2－二噻茂烷－4－基、四氫咪唑－2－基、四氫咪唑－4－基、四氫唑－2－基、四氫唑－4－基、四氫唑－5－基、四氫噻唑－2－基、四氫噻唑－4－基、四氫噻唑－5－基、1,3－二茂烷－2－基、1,3－二茂烷－4－基、1,3－噻茂烷－2－基、1,3－噻茂烷－4－基、1,3－噻茂烷－5－基、1,3－二噻茂烷－2－基、1,3－二噻茂烷－4－基、1,3,2－二噻茂烷－4－基。Carbon-attached 5-membered saturated ring, such as tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, tetrahydrothiophen-2-yl, tetrahydrothiophen-3-yl, tetrahydropyrrol-2-yl, tetrahydrogen Pyrrol-3-yl, tetrahydropyrazol-3-yl, tetrahydropyrazol-4-yl, tetrahydroiso Zyrom-3-yl, tetrahydroiso Zin-4-yl, tetrahydroiso Oxazol-5-yl, 1,2- Thioalkyl-3-yl, 1,2- Thiarman-4-yl, 1,2- Thiramal-5-yl, tetrahydroisothiazol-3-yl, tetrahydroisothiazol-4-yl, tetrahydroisothiazol-5-yl, 1,2-dithialan-3-yl, 1, 2-dithiazol-4-yl, tetrahydroimidazol-2-yl, tetrahydroimidazol-4-yl, tetrahydrogen Oxazol-2-yl, tetrahydrogen Zin-4-yl, tetrahydrogen Zyrid-5-yl, tetrahydrothiazol-2-yl, tetrahydrothiazol-4-yl, tetrahydrothiazol-5-yl, 1,3-di Molar-2-yl, 1,3-di Molar-4-yl, 1,3- Thiramane-2-yl, 1,3- Thiarmane-4-yl, 1,3- Thiramane-5-yl, 1,3-dithiamethane-2-yl, 1,3-dithiamoal-4-yl, 1,3,2-di Thiram-4-yl.

利用碳附接之6－員飽和環，如：四氫吲喃－2－基、四氫吲喃－3－基、四氫吲喃－4－基、哌啶－2－基、哌啶－3－基、哌啶－4－基、四氫硫吲喃－2－基、四氫硫吡喃－3－基、四氫硫吡喃－4－基、1,3－二烷－2－基、1,3－二烷－4－基、1,3－二烷－5－基、1,4－二烷－2－基、1,3－二噻烷－2－基、1,3－二噻烷－4－基、1,3－二噻烷－5－基、1,4－二噻烷－2－基、1,3－噻烷－2－基、1,3－噻烷－4－基、1,3－噻烷－5－基、1,3－噻烷－6－基、1,4－噻烷－2－基、1,4－噻烷－3－基、1,2－二噻烷－3－基、1,2－二噻烷－4－基、六氫嘧啶－2－基、六氫嘧啶－4－基、六氫嘧啶－5－基、六氫吡－2－基、六氫嗒－3－基、六氫嗒－4－基、四氫－1,3－－2－基、四氫－1,3－－4－基、四氫－1,3－－5－基、四氫－1,3－－6－基、四氫－1,3－噻－2－基、四氫－1,3－噻－4－基、四氫－1,3－噻－5－基、四氫－1,3－噻－6－基、四氫－1,4－噻－2－基、四氫－1,4－噻－3－基、四氫－1,4－－2－基、四氫－1,4－－3－基、四氫－1,2－－3－基、四氫－1,2－－4－基、四氫－1,2－－5－基、四氫－1,2－－6－基。6-membered saturated ring using carbon attachment, such as: tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, tetrahydrofuran-4-yl, piperidin-2-yl, piperidine- 3-yl, piperidin-4-yl, tetrahydrothiopyran-2-yl, tetrahydrothiopyran-3-yl, tetrahydrothiopyran-4-yl, 1,3-di Alkan-2-yl, 1,3-two Alk-4-yl, 1,3-two Alkan-5-yl, 1,4-two Alkan-2-yl, 1,3-dithiazin-2-yl, 1,3-dithiazin-4-yl, 1,3-dithiane-5-yl, 1,4-dithiane- 2-base, 1,3- Thiadi-2-yl, 1,3- Thiadi-4-yl, 1,3- Thiadi-5-yl, 1,3- Thiadiphenyl-6-yl, 1,4- Thiadi-2-yl, 1,4- Thial-3-yl, 1,2-dithiazol-3-yl, 1,2-dithiazol-4-yl, hexahydropyrimidin-2-yl, hexahydropyrimidin-4-yl, hexahydropyrimidine -5-yl, hexahydropyridyl -2-yl, hexahydroanthracene -3-yl, hexahydroindole -4-yl, tetrahydro-1,3- -2-yl, tetrahydro-1,3- -4-yl, tetrahydro-1,3- -5-based, tetrahydro-1,3- -6-based, tetrahydro-1,3-thiazide -2-yl, tetrahydro-1,3-thiazide -4-yl, tetrahydro-1,3-thiazide -5-based, tetrahydro-1,3-thiazide -6-based, tetrahydro-1,4-thiazide -2-yl, tetrahydro-1,4-thiazide -3-yl, tetrahydro-1,4- -2-yl, tetrahydro-1,4- -3-yl, tetrahydro-1,2- -3-yl, tetrahydro-1,2- -4-yl, tetrahydro-1,2- -5-based, tetrahydro-1,2- -6-based.

利用氮附接之5－員飽和環，如：四氫吡咯－1－基、四氫吡唑－1－基、四氫異唑－2－基、四氫異噻唑－2－基、四氫咪唑－1－基、四氫唑－3－基、四氫噻唑－3－基。5-membered saturated ring using nitrogen attachment, such as: tetrahydropyrrole-1-yl, tetrahydropyrazol-1-yl, tetrahydroiso Zin-2-yl, tetrahydroisothiazol-2-yl, tetrahydroimidazol-1-yl, tetrahydrogen Zyridin-3-yl, tetrahydrothiazol-3-yl.

利用氮附接之6－員飽和環，如：哌啶－1－基、六氫嘧啶－1－基、六氫吡－1－基、六氫嗒－1－基、四氫－1,3－－3－基、四氫－1,3－噻－3－基、四氫－1,4－噻－4－基、四氫－1,4－－4－基、四氫－1,2－－2－基。A 6-membered saturated ring using nitrogen attachment, such as: piperidin-1-yl, hexahydropyrimidin-1-yl, hexahydropyridyl -1-yl, hexahydroquinone -1-yl, tetrahydro-1,3- -3-yl, tetrahydro-1,3-thiazide -3-yl, tetrahydro-1,4-thiazide -4-yl, tetrahydro-1,4- -4-yl, tetrahydro-1,2- -2-yl.

利用碳附接之5－員部份不飽和環，如：2,3－二氫呋喃－2－基、2,3－二氫呋喃－3－基、2,5－二氫呋喃－2－基、2,5－二氫呋喃－3－基、4,5－二氫呋喃－2－基、4,5－二氫呋喃－3－基、2,3－二氫噻吩－2－基、2,3－二氫噻吩－3－基、2,5－二氫噻吩－2－基、2,5－二氫噻吩－3－基、4,5－二氫噻吩－2－基、4,5－二氫噻吩－3－基、2,3－二氫－1H－吡咯－2－基、2,3－二氫－1H－吡咯－3－基、2,5－二氫－1H－吡咯－2－基、2,5－二氫－1H－吡咯－3－基、4,5－二氫－1H－吡咯－2－基、4,5－二氫－1H－吡咯－3－基、3,4－二氫－2H－吡咯－2－基、3,4－二氫－2H－吡咯－3－基、3,4－二氫－5H－吡咯－2－基、3,4－二氫－5H－吡咯－3－基、4,5－二氫－1H－吡唑－3－基、4,5－二氫－1H－吡唑－4－基、4,5－二氫－1H－吡唑－5－基、2,5－二氫－1H－吡唑－3－基、2,5－二氫－1H－吡唑－4－基、2,5－二氫－1H－吡唑－5－基、4,5－二氫異唑－3－基、4,5－二氫異唑－4－基、4,5－二氫異唑－5－基、2,5－二氫異唑－3－基、2,5－二氫異唑－4－基、2,5－二氫異唑－5－基、2,3－二氫異唑－3－基、2,3－二氫異唑－4－基、2,3－二氫異唑－5－基、4,5－二氫異噻唑－3－基、4,5－二氫異噻唑－4－基、4,5－二氫異噻唑－5－基、2,5－二氫異噻唑－3－基、2,5－二氫異噻唑－4－基、2,5－二氫異噻唑－5－基、2,3－二氫異噻唑－3－基、2,3－二氫異噻唑－4－基、2,3－二氫異噻唑－5－基、△3 －1,2－二噻茂－3－基、△3 －1,2－二噻茂－4－基、△3 －1,2－二噻茂－5－基、4,5－二氫－1H－咪唑－2－基、4,5－二氫－1H－咪唑－4－基、4,5－二氫－1H－咪唑－5－基、2,5－二氫－1H－咪唑－2－基、2,5－二氫－1H－咪唑－4－基、2,5－二氫－1H－咪唑－5－基、2,3－二氫－1H－咪唑－2－基、2,3－二氫－1H－咪唑－4－基、4,5－二氫唑－2－基、4,5－二氫唑－4－基、4,5－二氫唑－5－基、2,5－二氫唑－2－基、2,5－二氫唑－4－基、2,5－二氫唑－5－基、2,3－二氫唑－2－基、2,3－二氫唑－4－基、2,3－二氫唑－5－基、4,5－二氫噻唑－2－基、4,5－二氫噻唑－4－基、4,5－二氫噻唑－5－基、2,5－二氫噻唑－2－基、2,5－二氫噻唑－4－基、2,5－二氫噻唑－5－基、2,3－二氫噻唑－2－基、2,3－二氫噻唑－4－基、2,3－二氫噻唑－5－基、1,3－二茂－2－基、1,3－二茂－4－基、1,3－二噻茂－2－基、1,3－二噻茂－4－基、1,3－噻茂－2－基、1,3－噻茂－4－基、1,3－噻茂－5－基、1,2,3－△2 －二噻唑啉－4－基、1,2,3－△2 －二唑啉－5－基、1,2,4－△4 －二唑啉－3－基、1,2,4－△4 －二唑啉－5－基、1,2,4－△2 －二唑啉－3－基、1,2,4－△2 －二唑啉－5－基、1,2,4－△3 －二唑啉－3－基、1,2,4－△3 －二唑啉－5－基、1,3,4－△2 －二唑啉－2－基、1,3,4－△2 －二唑啉－5－基、1,3,4－△3 －二唑啉－2－基、1,3,4－二唑啉－2－基、1,2,4－△4 －噻二唑啉－3－基、1,2,4－△4 －噻二唑啉－5－基、1,2,4－△3 －噻二唑啉－3－基、1,2,4－△3 －噻二唑啉－5－基、1,2,4－△2 －噻二唑啉－3－基、1,2,4－△2 －噻二唑啉－5－基、1,3,4－△2 －噻二唑啉－2－基、1,3,4－△2 －噻二唑啉－5－基、1,3,4－△3 －噻二唑啉－2－基、1,3,4－噻二唑啉－2－基、1,2,3－△2 －***啉－4－基、1,2,3－△2 －***啉－5－基、1,2,4－△2 －***啉－3－基、1,2,4－△2 －***啉－5－基、1,2,4－△3 －***啉－3－基、1,2,4－△3 －***啉－5－基、1,2,4－△1 －***啉－2－基、1,2,4－***啉－3－基、3H－1,2,4－二噻唑－5－基、2H－1,3,4－二噻唑－5－基、2H－1,3,4－噻唑－5－基。5-membered partially unsaturated ring attached by carbon, such as: 2,3-dihydrofuran-2-yl, 2,3-dihydrofuran-3-yl, 2,5-dihydrofuran-2- Base, 2,5-dihydrofuran-3-yl, 4,5-dihydrofuran-2-yl, 4,5-dihydrofuran-3-yl, 2,3-dihydrothiophen-2-yl, 2,3-Dihydrothiophen-3-yl, 2,5-dihydrothiophen-2-yl, 2,5-dihydrothiophen-3-yl, 4,5-dihydrothiophen-2-yl, 4, 5-Dihydrothiophen-3-yl, 2,3-dihydro-1H-pyrrol-2-yl, 2,3-dihydro-1H-pyrrol-3-yl, 2,5-dihydro-1H-pyrrole -2-yl, 2,5-dihydro-1H-pyrrol-3-yl, 4,5-dihydro-1H-pyrrol-2-yl, 4,5-dihydro-1H-pyrrol-3-yl, 3,4-Dihydro-2H-pyrrol-2-yl, 3,4-dihydro-2H-pyrrol-3-yl, 3,4-dihydro-5H-pyrrol-2-yl, 3,4-di Hydrogen-5H-pyrrol-3-yl, 4,5-dihydro-1H-pyrazol-3-yl, 4,5-dihydro-1H-pyrazol-4-yl, 4,5-dihydro-1H -pyrazol-5-yl, 2,5-dihydro-1H-pyrazol-3-yl, 2,5-dihydro-1H-pyrazole-4 -yl, 2,5-dihydro-1H-pyrazol-5-yl, 4,5-dihydroiso Zyrom-3-yl, 4,5-dihydroiso Zin-4-yl, 4,5-dihydroiso Oxazol-5-yl, 2,5-dihydroiso Zyrid-3-yl, 2,5-dihydroiso Zin-4-yl, 2,5-dihydroiso Oxazol-5-yl, 2,3-dihydroiso Zyrom-3-yl, 2,3-dihydroiso Zin-4-yl, 2,3-dihydroiso Zyrid-5-yl, 4,5-dihydroisothiazol-3-yl, 4,5-dihydroisothiazol-4-yl, 4,5-dihydroisothiazol-5-yl, 2,5-di Hydroisothiazol-3-yl, 2,5-dihydroisothiazol-4-yl, 2,5-dihydroisothiazol-5-yl, 2,3-dihydroisothiazol-3-yl, 2,3 -Dihydroisothiazol-4-yl, 2,3-dihydroisothiazol-5-yl, Δ 3 -1,2-dithiazolyl-3-yl, Δ 3 -1 ,2-dithiazole-4 -yl, Δ 3 -1,2-dithiato-5-yl, 4,5-dihydro-1H-imidazol-2-yl, 4,5-dihydro-1H-imidazol-4-yl, 4, 5-Dihydro-1H-imidazol-5-yl, 2,5-dihydro-1H-imidazol-2-yl, 2,5-dihydro-1H-imidazol-4-yl, 2,5-dihydro- 1H-imidazole-5-yl, 2,3-dihydro-1H-imidazol-2-yl, 2,3-dihydro-1H-imidazol-4-yl, 4,5-dihydro Zin-2-yl, 4,5-dihydro Zin-4-yl, 4,5-dihydro Oxazol-5-yl, 2,5-dihydro Zin-2-yl, 2,5-dihydro Zin-4-yl, 2,5-dihydro Oxazol-5-yl, 2,3-dihydrogen Zin-2-yl, 2,3-dihydro Zin-4-yl, 2,3-dihydrogen Zyrid-5-yl, 4,5-dihydrothiazol-2-yl, 4,5-dihydrothiazol-4-yl, 4,5-dihydrothiazol-5-yl, 2,5-dihydrothiazole- 2-Based, 2,5-dihydrothiazol-4-yl, 2,5-dihydrothiazol-5-yl, 2,3-dihydrothiazol-2-yl, 2,3-dihydrothiazole-4- Base, 2,3-dihydrothiazole-5-yl, 1,3-di Mao-2-yl, 1,3-two Methyl-4-yl, 1,3-dithiato-2-yl, 1,3-dithiato-4-yl, 1,3- Thio-2-yl, 1,3- Thio-4-yl, 1,3- Thio-5-yl, 1,2,3-△ 2 - Dithiazolin-4-yl, 1,2,3-△ 2 - Diazoline-5-yl, 1,2,4-△ 4 - Diazolin-3-yl, 1,2,4-△ 4 - Diazoline-5-yl, 1,2,4-△ 2 - Diazolin-3-yl, 1,2,4-△ 2 - Diazoline-5-yl, 1,2,4-△ 3 - Diazolin-3-yl, 1,2,4-△ 3 - Diazolin-5-yl, 1,3,4-△ 2 - Diazolin-2-yl, 1,3,4-△ 2 - Diazolin-5-yl, 1,3,4-△ 3 - Diazolin-2-yl, 1,3,4- Diazolin-2-yl, 1,2,4-△ 4 -thiadiazolin-3-yl, 1,2,4-△ 4 -thiadiazolin-5-yl, 1,2,4- Δ 3 -thiadiazolin-3-yl, 1,2,4-△ 3 -thiadiazolin-5-yl, 1,2,4-△ 2 -thiadiazolin-3-yl, 1, 2,4-△ 2 -thiadiazolin-5-yl, 1,3,4-△ 2 -thiadiazolin-2-yl, 1,3,4-△ 2 -thiadiazoline-5- 1,1,3,4-△ 3 -thiadiazolin-2-yl, 1,3,4-thiadiazolin-2-yl, 1,2,3-△ 2 -triazolin-4- 1,1,2,3-△ 2 -triazolin-5-yl, 1,2,4-△ 2 -triazolin-3-yl, 1,2,4-△ 2 -triazoline-5 -yl, 1,2,4-△ 3 -triazolin-3-yl, 1,2,4-△ 3 -triazolin-5-yl, 1,2,4-Δ 1 -triazoline - 2-Based, 1,2,4-triazolin-3-yl, 3H-1,2,4-dithiazol-5-yl, 2H-1,3,4-dithiazol-5-yl, 2H- 1,3,4- Thiazol-5-yl.

利用碳附接之6－員部份不飽和環，如：2H－3,4－二氫比喃－6－基、2H－3,4－二氫吡喃－5－基、2H－3,4－二氫吡喃－4－基、2H－3,4－二氫吡喃－3－基、2H－3,4－二氫吡喃－2－基、2H－3,4－二氫硫吡喃－6－基、2H－3,4－二氫硫吡喃－5－基、2H－3,4－二氫硫吡喃－4－基、2H－3,4－二氫硫吡喃－3－基、2H－3,4－二氫硫吡喃－2－基、1,2,3,4－四氫吡啶－6－基、1,2,3,4－四氫吡啶－5－基、1,2,3,4－四氫吡啶－4－基、1,2,3,4－四氫吡啶－3－基、1,2,3,4－四氫吡啶－2－基、2H－5,6－二氫吡喃－2－基、2H－5,6－二氫吡喃－3－基、2H－5,6－二氫吡喃－4－基、2H－5,6－二氫吡喃－5－基、2H－5,6－二氫吡喃－6－基、2H－5,6－二氫硫吡喃－2－基、2H－5,6－二氫硫吡喃－3－基、2H－5,6－二氫硫吡喃－4－基、2H－5,6－二氫硫吡喃－5－基、2H－5,6－二氫硫吡喃－6－基、1,2,5,6－四氫吡啶－2－基、1,2,5,6－四氫吡啶－3－基、1,2,5,6－四氫吡啶－4－基、1,2,5,6－四氫吡啶－5－基、1,2,5,6－四氫吡啶－6－基、2,3,4,5－四氫吡啶－2－基、2,3,4,5－四氫吡啶－3－基、2,3,4,5－四氫吡啶－4－基、2,3,4,5－四氫吡啶－5－基、2,3,4,5－四氫吡啶－6－基、4H－吡喃－2－基、4H－吡喃－3－基－、4H－吡喃－4－基、4H－硫吡喃－2－基、4H－硫吡喃－3－基、4H－硫吡喃－4－基、1,4－二氫吡啶－2－基、1,4－二氫吡啶－3－基、1,4－二氫吡啶－4－基、2H－吡喃－2－基、2H－吡喃－3－基、2H－吡喃－4－基、2H－吡喃－5－基、2H－吡喃－6－基、2H－硫吡喃－2－基、2H－硫吡喃－3－基、2H－硫吡喃－4－基、2H－硫吡喃－5－基、2H－硫吡喃－6－基、1,2－二氫吡啶－2－基、1,2－二氫吡啶－3－基、1,2－二氫吡啶－4－基、1,2－二氫吡啶－5－基、1,2－二氫吡啶－6－基、3,4－二氫吡啶－2－基、3,4－二氫吡啶－3－基、3,4－二氫吡啶－4－基、3,4－二氫吡啶－5－基、3,4－二氫吡啶－6－基、2,5－二氫吡啶－2－基、2,5－二氫吡啶－3－基、2,5－二氫吡啶－4－基、2,5－二氫吡啶－5－基、2,5－二氫吡啶－6－基、2,3－二氫吡啶－2－基、2,3－二氫吡啶－3－基、2,3－二氫吡啶－4－基、2,3－二氫吡啶－5－基、2,3－二氫吡啶－6－基、2H－5,6－二氫－1,2－－3－基、2H－5,6－二氫－1,2－－4－基、2H－5,6－二氫－1,2－－5－基、2H－5,6－二氫－1,2－－6－基、2H－5,6－二氫－1,2－噻－3－基、2H－5,6－二氫－1,2－噻－4－基、2H－5,6－二氫－1,2－噻－5－基、2H－5,6－二氫－1,2－噻－6－基、4H－5,6－二氫－1,2－－3－基、4H－5,6－二氫－1,2－－4－基、4H－5,6－二氫－1,2－－5－基、4H－5,6－二氫－1,2－－6－基、4H－5,6－二氫－1,2－噻－3－基、4H－5,6－二氫－1,2－噻－4－基、4H－5,6－二氫－1,2－噻－5－基、4H－5,6－二氫－1,2－噻－6－基、2H－3,6－二氫－1,2－－3－基、2H－3,6－二氫－1,2－－4－基、2H－3,6－二氫－1,2－－5－基、2H－3,6－二氫－1,2－－6－基、2H－3,6－二氫－1,2－噻－3－基、2H－3,6－二氫－1,2－噻－4－基、2H－3,6－二氫－1,2－噻－5－基、2H－3,6－二氫－1,2－噻－6－基、2H－3,4－二氫－1,2－－3－基、2H－3,4－二氫－1,2－－4－基、2H－3,4－二氫－1,2－－5－基、2H－3,4－二氫－1,2－－6－基、2H－3,4－二氫－1,2噻－3－基、2H－3,4－二氫－1,2－噻－4－基、2H－3,4－二氫－1,2－噻－5－基、2H－3,4－二氫－1,2－噻－6－基、2,3,4,5－四氫嗒－3－基、2,3,4,5－四氫嗒－4－基、2,3,4,5－四氫嗒－5－基、2,3,4,5－四氫嗒－6－基、3,4,5,6－四氫嗒－3－基、3,4,5,6－四氫嗒－4－基、1,2,5,6－四氫嗒－3－基、1,2,5,6－四氫嗒－4－基、1,2,5,6－四氫嗒－5－基、1,2,5,6－四氫嗒－6－基、1,2,3,6－四氫嗒－3－基、1,2,3,6－四氫嗒－4－基、4H－5,6－二氫－1,3－－2－基、4H－5,6－二氫－1,3－－4－基、4H－5,6－二氫－1,3－－5－基、4H－5,6－二氫－1,3－－6－基、4H－5,6－二氫－1,3－噻－2－基、4H－5,6－二氫－1,3－噻－4－基、4H－5,6－二氫－1,3－噻－5－基、4H－5,6－二氫－1,3－噻－6－基、3,4,5－6－四氫嘧啶－2－基、3,4,5,6－四氫嘧啶－4－基、3,4,5,6－四氫嘧啶－5－基、3,4,5,6－四氫嘧啶－6－基、1,2,3,4－四氫吡－2－基、1,2,3,4－四氫吡－5－基、1,2,3,4－四氫嘧啶－2－基、1,2,3,4－四氫嘧啶－4－基、1,2,3,4－四氫嘧啶－5－基、1,2,3,4－四氫嘧啶－6－基、2,3－二氫－1,4－噻－2－基、2,3－二氫－1,4－噻－3－基、2,3－二氫－1,4－噻－5－基、2,3－二氫－1,4－噻－6－基、2H－1,2－－3－基、2H－1,2－－4－基、2H－1,2－－5－基、2H－1,2－－6－基、2H－1,2噻－3－基、2H－1,2－噻－4－基、2H－1,2－噻－5－基、2H－1,2－噻－6－基、4H－1,2－－3－基、4H－1,2－－4－基、4H－1,2－－5－基、4H－1,2－－6－基、4H－1,2－噻－3－基、4H－1,2－噻－4－基、4H－1,2－噻－5－基、4H－1,2－噻－6－基、6H－1,2－－3－基、6H－1,2－－4－基、6H－1,2－－5－基、6H－1,2－－6－基、6H－1,2－噻－3－基、6H－1,2－噻－4－基、6H－1,2－噻－5－基、6H－1,2－噻－6－基、2H－1,3－－2－基、2H－1,3－－4－基、2H－1,3－－5－基、2H－1,3－－6－基、2H－1,3－噻－2－基、2H－1,3－噻－4－基、2H－1,3－噻－5－基、2H－1,3－噻－6－基、4H－1,3－－2－基、4H－1,3－－4－基、4H－1,3－－5－基、4H－1,3－－6－基、4H－1,3－噻－2－基、4H－1,3－噻－4－基、4H－1,3－噻－5－基、4H－1,3－噻－6－基、6H－1,3－－2－基、6H－1,3－－4－基、6H－1,3－－5－基、6H－1,3－－6－基、6H－1,3－噻－2－基、6H－1,3－－4－基、6H－1,3－－5－基、6H－1,3－噻－6－基、2H－1,4－－2－基、2H－1,4－－3－基、2H－1,4－－5－基、2H－1,4－－6－基、2H－1,4－噻－2－基、2H－1,4－噻－3－基、2H－1,4－噻－5－基、2H－1,4－噻－6－基、4H－1,4－－2－基、4H－1,4－－3－基、4H－1,4－噻－2－基、4H－1,4－噻－3－基、1,4－二氫嗒－3－基、1,4－二氫嗒－4－基、1,4－二氫嗒－5－基、1,4－二氫嗒－6－基、1,4－二氫吡－2－基、1,2－二氫吡－2－基、1,2－二氫吡－3－基、1,2－二氫吡－5－基、1,2－二氫吡－6－基、1,4－二氫嘧啶－2－基、1,4－二氫嘧啶－4－基、1,4－二氫嘧啶－5－基、1,4－二氫嘧啶－6－基、3,4－二氫嘧啶－2－基、3,4－二氫嘧啶－4－基、3,4－二氫嘧啶－5－基或3,4－二氫嘧啶－6－基。A 6-membered partially unsaturated ring attached by carbon, such as 2H-3,4-dihydropyran-6-yl, 2H-3,4-dihydropyran-5-yl, 2H-3, 4-Dihydropyran-4-yl, 2H-3,4-dihydropyran-3-yl, 2H-3,4-dihydropyran-2-yl, 2H-3,4-dihydrogen Pyran-6-yl, 2H-3,4-dihydrothiopyran-5-yl, 2H-3,4-dihydrothiopyran-4-yl, 2H-3,4-dihydrothiopyran 3-yl, 2H-3,4-dihydrothiapyran-2-yl, 1,2,3,4-tetrahydropyridin-6-yl, 1,2,3,4-tetrahydropyridine-5 -yl, 1,2,3,4-tetrahydropyridin-4-yl, 1,2,3,4-tetrahydropyridin-3-yl, 1,2,3,4-tetrahydropyridin-2-yl 2H-5,6-dihydropyran-2-yl, 2H-5,6-dihydropyran-3-yl, 2H-5,6-dihydropyran-4-yl, 2H-5, 6-Dihydropyran-5-yl, 2H-5,6-dihydropyran-6-yl, 2H-5,6-dihydrothiopyran-2-yl, 2H-5,6-dihydro Thiopyran-3-yl, 2H-5,6-dihydrothiopyran-4-yl, 2H-5,6-dihydrothiopyran-5-yl, 2H-5,6-dihydrothiopyran Nor-6-yl, 1,2,5,6-tetrahydropyridine 2-Based, 1,2,5,6-tetrahydropyridin-3-yl, 1,2,5,6-tetrahydropyridin-4-yl, 1,2,5,6-tetrahydropyridine-5- 1,1,2,5,6-tetrahydropyridin-6-yl, 2,3,4,5-tetrahydropyridin-2-yl, 2,3,4,5-tetrahydropyridin-3-yl, 2,3,4,5-tetrahydropyridin-4-yl, 2,3,4,5-tetrahydropyridin-5-yl, 2,3,4,5-tetrahydropyridin-6-yl, 4H- Pyran-2-yl, 4H-pyran-3-yl-, 4H-pyran-4-yl, 4H-thiopyran-2-yl, 4H-thiopyran-3-yl, 4H-thiopyridyl喃-4-yl, 1,4-dihydropyridin-2-yl, 1,4-dihydropyridin-3-yl, 1,4-dihydropyridin-4-yl, 2H-pyran-2-yl , 2H-pyran-3-yl, 2H-pyran-4-yl, 2H-pyran-5-yl, 2H-pyran-6-yl, 2H-thiopyran-2-yl, 2H-sulfur Pyran-3-yl, 2H-thiopyran-4-yl, 2H-thiopyran-5-yl, 2H-thiopyran-6-yl, 1,2-dihydropyridin-2-yl, 1 , 2-dihydropyridin-3-yl, 1,2-dihydropyridin-4-yl, 1,2-dihydropyridin-5-yl, 1,2-dihydropyridin-6-yl, 3,4 -dihydrogen Pyridin-2-yl, 3,4-dihydropyridin-3-yl, 3,4-dihydropyridin-4-yl, 3,4-dihydropyridin-5-yl, 3,4-dihydropyridine- 6-yl, 2,5-dihydropyridin-2-yl, 2,5-dihydropyridin-3-yl, 2,5-dihydropyridin-4-yl, 2,5-dihydropyridine-5- , 2,5-dihydropyridin-6-yl, 2,3-dihydropyridin-2-yl, 2,3-dihydropyridin-3-yl, 2,3-dihydropyridin-4-yl, 2,3-Dihydropyridin-5-yl, 2,3-dihydropyridin-6-yl, 2H-5,6-dihydro-1,2- -3-yl, 2H-5,6-dihydro-1,2- 4-yl, 2H-5,6-dihydro-1,2- -5-yl, 2H-5,6-dihydro-1,2- -6-yl, 2H-5,6-dihydro-1,2-thia -3-yl, 2H-5,6-dihydro-1,2-thia 4-yl, 2H-5,6-dihydro-1,2-thia -5-yl, 2H-5,6-dihydro-1,2-thia -6-yl, 4H-5,6-dihydro-1,2- -3-yl, 4H-5,6-dihydro-1,2- 4-yl, 4H-5,6-dihydro-1,2- -5-yl, 4H-5,6-dihydro-1,2- -6-yl, 4H-5,6-dihydro-1,2-thia -3-yl, 4H-5,6-dihydro-1,2-thia 4-yl, 4H-5,6-dihydro-1,2-thia -5-yl, 4H-5,6-dihydro-1,2-thia -6-yl, 2H-3,6-dihydro-1,2- -3-yl, 2H-3,6-dihydro-1,2- 4-yl, 2H-3,6-dihydro-1,2- -5-yl, 2H-3,6-dihydro-1,2- -6-yl, 2H-3,6-dihydro-1,2-thia -3-yl, 2H-3,6-dihydro-1,2-thia 4-yl, 2H-3,6-dihydro-1,2-thia -5-yl, 2H-3,6-dihydro-1,2-thia -6-based, 2H-3,4-dihydro-1,2- -3-yl, 2H-3,4-dihydro-1,2- 4-yl, 2H-3,4-dihydro-1,2- -5-yl, 2H-3,4-dihydro-1,2- -6-based, 2H-3,4-dihydro-1,2-thiazide -3-yl, 2H-3,4-dihydro-1,2-thia 4-yl, 2H-3,4-dihydro-1,2-thia -5-yl, 2H-3,4-dihydro-1,2-thia -6-based, 2,3,4,5-tetrahydroanthracene -3-yl, 2,3,4,5-tetrahydroanthracene 4-yl, 2,3,4,5-tetrahydroanthracene -5-yl, 2,3,4,5-tetrahydroanthracene -6-based, 3,4,5,6-tetrahydroanthracene -3-yl, 3,4,5,6-tetrahydroanthracene 4-yl, 1,2,5,6-tetrahydroanthracene -3-yl, 1,2,5,6-tetrahydroanthracene 4-yl, 1,2,5,6-tetrahydroanthracene -5-yl, 1,2,5,6-tetrahydroanthracene -6-yl, 1,2,3,6-tetrahydroanthracene -3-yl, 1,2,3,6-tetrahydroanthracene 4-yl, 4H-5,6-dihydro-1,3- -2-yl, 4H-5,6-dihydro-1,3- 4-yl, 4H-5,6-dihydro-1,3- -5-yl, 4H-5,6-dihydro-1,3- -6-based, 4H-5,6-dihydro-1,3-thiazide -2-yl, 4H-5,6-dihydro-1,3-thiazide 4-yl, 4H-5,6-dihydro-1,3-thiazide -5-yl, 4H-5,6-dihydro-1,3-thiazide -6-yl, 3,4,5-6-tetrahydropyrimidin-2-yl, 3,4,5,6-tetrahydropyrimidin-4-yl, 3,4,5,6-tetrahydropyrimidin-5 -yl, 3,4,5,6-tetrahydropyrimidin-6-yl, 1,2,3,4-tetrahydropyridyl -2-yl, 1,2,3,4-tetrahydropyridyl -5-yl, 1,2,3,4-tetrahydropyrimidin-2-yl, 1,2,3,4-tetrahydropyrimidin-4-yl, 1,2,3,4-tetrahydropyrimidine-5 -yl, 1,2,3,4-tetrahydropyrimidin-6-yl, 2,3-dihydro-1,4-thiazide -2-yl, 2,3-dihydro-1,4-thiazide -3-yl, 2,3-dihydro-1,4-thiazide -5-yl, 2,3-dihydro-1,4-thiazide -6-based, 2H-1,2- -3-yl, 2H-1,2- -4-yl, 2H-1,2- -5-based, 2H-1,2- -6-based, 2H-1, 2 thiophene -3-yl, 2H-1,2-thia 4-yl, 2H-1,2-thia -5-based, 2H-1,2-thia -6-based, 4H-1,2- -3-yl, 4H-1,2- -4-base, 4H-1,2- -5-based, 4H-1,2- -6-based, 4H-1,2-thiazide -3-yl, 4H-1,2-thia -4-yl, 4H-1,2-thiazide -5-based, 4H-1,2-thia -6-based, 6H-1,2- -3-yl, 6H-1,2- -4-yl, 6H-1,2- -5-based, 6H-1,2- -6-based, 6H-1,2-thiazide -3-yl, 6H-1,2-thia -4-yl, 6H-1,2-thiazide -5-based, 6H-1,2-thia -6-based, 2H-1,3- -2-yl, 2H-1,3- -4-yl, 2H-1,3- -5-based, 2H-1,3- -6-based, 2H-1,3-thiazide -2-yl, 2H-1,3-thiazide -4-yl, 2H-1,3-thiazide -5-based, 2H-1,3-thiazide -6-based, 4H-1,3- -2-base, 4H-1,3- -4-yl, 4H-1,3- -5-based, 4H-1,3- -6-based, 4H-1,3-thiazide -2-yl, 4H-1,3-thiazide -4-yl, 4H-1,3-thiazide -5-based, 4H-1,3-thiazide -6-based, 6H-1,3- -2-yl, 6H-1,3- -4-base, 6H-1,3- -5-based, 6H-1,3- -6-based, 6H-1,3-thiazide -2-yl, 6H-1,3- -4-base, 6H-1,3- -5-based, 6H-1,3-thiazide -6-based, 2H-1,4- -2-yl, 2H-1,4- -3-yl, 2H-1,4- -5-based, 2H-1,4- -6-based, 2H-1,4-thiazide -2-yl, 2H-1,4-thiazide -3-yl, 2H-1,4-thiazide -5-yl, 2H-1,4-thiazide -6-based, 4H-1,4- -2-yl, 4H-1,4- -3-yl, 4H-1,4-thiazide -2-yl, 4H-1,4-thiazide -3-yl, 1,4-dihydroindole -3-yl, 1,4-dihydroindole 4-yl, 1,4-dihydroindole -5-yl, 1,4-dihydroanthracene -6-based, 1,4-dihydropyridyl -2-yl, 1,2-dihydropyridyl -2-yl, 1,2-dihydropyridyl -3-yl, 1,2-dihydropyridyl -5-yl, 1,2-dihydropyridyl -6-yl, 1,4-dihydropyrimidin-2-yl, 1,4-dihydropyrimidin-4-yl, 1,4-dihydropyrimidin-5-yl, 1,4-dihydropyrimidine-6 -yl, 3,4-dihydropyrimidin-2-yl, 3,4-dihydropyrimidin-4-yl, 3,4-dihydropyrimidin-5-yl or 3,4-dihydropyrimidin-6-yl .

利用氮附接之5－員部份不飽和環，如：2,3－二氫－1H－吡咯－1－基、2,5－二氫－1H－吡咯－1－基、4,5－二氫－1H－吡唑－1－基、2,5－二氫－1H－吡唑－1－基、2,3－二氫－1H－吡唑－1－基、2,5－二氫異唑－2－基、2,3－二氫異唑－2－基、2,5－二氫異噻唑－2－基、2,3－二氫異唑－2－基、4,5－二氫－1H－咪唑－1－基、2,5－二氫－1H－咪唑－1－基、2,3－二氫－1H－咪唑－1－基、2,3－二氫唑－3－基、2,3－二氫噻唑－3－基、1,2,4－△4 －二唑啉－2－基、1,2,4－△2 －二唑啉－4－基、1,2,4－△3 －二唑啉－2－基、1,3,4－△2 －二唑啉－4－基、1,2,4－△5 －噻二唑啉－2－基、1,2,4－△3 －噻二唑啉－2－基、1,2,4－△2 －噻二唑啉－4－基、1,3,4－△2 －噻二唑啉－4－基、1,2,3－△2 －***啉－1－基、1,2,4－△2 －***啉－1－基、1,2,4－△2 －***啉－4－基、1,2,4－△3 －***啉－1－基、1,2,4－△1 －***啉－4－基。5-membered partially unsaturated ring attached by nitrogen, such as: 2,3-dihydro-1H-pyrrol-1-yl, 2,5-dihydro-1H-pyrrol-1-yl, 4,5- Dihydro-1H-pyrazol-1-yl, 2,5-dihydro-1H-pyrazol-1-yl, 2,3-dihydro-1H-pyrazol-1-yl, 2,5-dihydro different Zin-2-yl, 2,3-dihydroiso Zin-2-yl, 2,5-dihydroisothiazol-2-yl, 2,3-dihydroiso Zin-2-yl, 4,5-dihydro-1H-imidazol-1-yl, 2,5-dihydro-1H-imidazol-1-yl, 2,3-dihydro-1H-imidazol-1-yl 2,3-dihydrogen Zyridin-3-yl, 2,3-dihydrothiazol-3-yl, 1,2,4-△ 4 - Diazolin-2-yl, 1,2,4-△ 2 - Diazolin-4-yl, 1,2,4-△ 3 - Diazolin-2-yl, 1,3,4-△ 2 - Diazolin-4-yl, 1,2,4-△ 5 -thiadiazolin-2-yl, 1,2,4-△ 3 -thiadiazolin-2-yl, 1,2,4- Δ 2 -thiadiazolin-4-yl, 1,3,4-△ 2 -thiadiazolin-4-yl, 1,2,3-△ 2 -triazolin-1-yl, 1,2 , 4-△ 2 -triazolin-1-yl, 1,2,4-△ 2 -triazolin-4-yl, 1,2,4-△ 3 -triazolin-1-yl, 1, 2,4-Δ 1 -triazolin-4-yl.

利用氮附接之6－員部份不飽和環，如：1,2,3,4－四氫吡啶－1－基、1,2,5,6－四氫吡啶－1－基、1,4－二氫吡啶－1－基、1,2－二氫吡啶－1－基、2H－5,6－二氫－1,2－－2－基、2H－5,6－二氫－1,2－噻－2－基、2H－3,6－二氫－1,2－－2－基、2H－3,6－二氫－1,2－噻－2－基、2H－3,4－二氫－1,2－－2－基、2H－3,4－二氫－1,2－噻－2－基、2,3,4,5－四氫嗒－2－基、1,2,5,6－四氫嗒－1－基、1,2,5,6－四氫嗒－2－基、1,2,3,6－四氫嗒－1－基、3,4,5,6－四氫嘧啶－3－基、1,2,3,4－四氫吡－1－基、1,2,3,4－四氫嘧啶－1－基、1,2,3,4－四氫嘧啶－3－基、2,3－二氫－1,4－嘧－4－基、2H－1,2－－2－基、2H－1,2－噻－2－基、4H－1,4－－4－基、4H－1,4－噻－4－基、1,4－二氫嗒－1－基、1,4－二氫吡－1－基、1,2－二氫吡－1－基、1,4－二氫嘧啶－1－基或3,4－二氫嘧啶－3－基。a 6-membered partially unsaturated ring attached by nitrogen, such as: 1,2,3,4-tetrahydropyridin-1-yl, 1,2,5,6-tetrahydropyridin-1-yl, 1, 4-Dihydropyridin-1-yl, 1,2-dihydropyridin-1-yl, 2H-5,6-dihydro-1,2- -2-yl, 2H-5,6-dihydro-1,2-thia -2-yl, 2H-3,6-dihydro-1,2- -2-yl, 2H-3,6-dihydro-1,2-thia -2-yl, 2H-3,4-dihydro-1,2- -2-yl, 2H-3,4-dihydro-1,2-thia -2-yl, 2,3,4,5-tetrahydroanthracene -2-yl, 1,2,5,6-tetrahydroanthracene -1-yl, 1,2,5,6-tetrahydroanthracene -2-yl, 1,2,3,6-tetrahydroanthracene -1-yl, 3,4,5,6-tetrahydropyrimidin-3-yl, 1,2,3,4-tetrahydropyridyl -1-yl, 1,2,3,4-tetrahydropyrimidin-1-yl, 1,2,3,4-tetrahydropyrimidin-3-yl, 2,3-dihydro-1,4-pyrimidine -4-yl, 2H-1,2- -2-yl, 2H-1,2-thia -2-yl, 4H-1,4- -4-yl, 4H-1,4-thiazide 4-yl, 1,4-dihydroindole -1-yl, 1,4-dihydropyridyl -1-yl, 1,2-dihydropyridyl 1-yl, 1,4-dihydropyrimidin-1-yl or 3,4-dihydropyrimidin-3-yl.

利用碳附接之5－員雜芳香環，其通常具有1、2、3或4個氮原子或一個氧或硫原子，且若適當時，具有1、2或3個氮原子作為環組員，如：2－呋喃基、3－呋喃基、2－噻吩基、3－噻吩基、吡咯－2－基、吡咯－3－基、吡唑－3－基、吡唑－4－基、異唑－3－基、異唑－4－基、異唑－5－基、異噻唑－3－基、異噻唑－4－基、異噻唑－5－基、咪唑－2－基、咪唑－4－基、唑－2－基、唑－4－基、唑－5－基、噻唑－2－基、噻唑－4－基、噻唑－5－基、1,2,3－二唑－4－基、1,2,3－二唑－5－基、1,2,4－二唑－3－基、1,2,4,－二唑－5－基、1,3,4－二唑－2－基、1,2,3－噻二唑－4－基、1,2,3－噻二唑－5－基、1,2,4－噻二唑－3－基、1,2,4－噻二唑－5－基、1,3,4－噻二唑基－2－基、1,2,3－***－4－基、1,2,4－***－3－基、四唑－5－基。a carbon-attached 5-membered heteroaromatic ring which typically has 1, 2, 3 or 4 nitrogen atoms or an oxygen or sulfur atom and, if appropriate, 1, 2 or 3 nitrogen atoms as ring members, Such as: 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, pyrrol-2-yl, pyrrol-3-yl, pyrazol-3-yl, pyrazol-4-yl, iso Zyrom-3-yl, different Azol-4-yl, different Zyrid-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, imidazol-2-yl, imidazol-4-yl, Zin-2-yl, Zin-4-yl, Zyrid-5-yl, thiazol-2-yl, thiazol-4-yl, thiazol-5-yl, 1,2,3- Diazol-4-yl, 1,2,3- Diazol-5-yl, 1,2,4- Diazol-3-yl, 1,2,4,- Diazol-5-yl, 1,3,4- Diazol-2-yl, 1,2,3-thiadiazol-4-yl, 1,2,3-thiadiazol-5-yl, 1,2,4-thiadiazol-3-yl, 1 , 2,4-thiadiazol-5-yl, 1,3,4-thiadiazolyl-2-yl, 1,2,3-triazol-4-yl, 1,2,4-triazole- 3-based, tetrazol-5-yl.

利用碳附接之6－員雜芳香環，其通常具有1、2、3或4個氮原子作為環組員，如：吡啶－2－基、吡啶－3－基、吡啶－4－基、嗒－3－基、嗒－4－基、嘧啶－2－基、嘧啶－4－基、嘧啶－5－基、吡－2－基、1,3,5－三－2－基、1,2,4－三－3－基、1,2,4－三－5－基、1,2,4－三－6－基、1,2,4,5－四－3－基。A carbon-attached 6-membered heteroaromatic ring, which typically has 1, 2, 3 or 4 nitrogen atoms as a ring member, such as pyridin-2-yl, pyridin-3-yl, pyridin-4-yl, fluorene -3-yl, 嗒 4-yl, pyrimidin-2-yl, pyrimidin-4-yl, pyrimidin-5-yl, pyridyl -2-base, 1,3,5-three -2-base, 1,2,4-three -3-yl, 1,2,4-three -5-base, 1,2,4-three -6-base, 1, 2, 4, 5-four -3- base.

利用氮原子附接之5－員雜芳香環，其通常具有1、2、3或4個氮原子作為環組員，如：吡咯－1－基、吡唑－1－基、咪唑－1－基、1,2,3－***－1－基、1,2,4－***－1－基、四唑－1－基。A 5-membered heteroaromatic ring attached by a nitrogen atom, which usually has 1, 2, 3 or 4 nitrogen atoms as a ring member, such as pyrrol-1-yl, pyrazol-1-yl, imidazol-1-yl 1,2,3-triazol-1-yl, 1,2,4-triazol-1-yl, tetrazol-1-yl.

或包含如上述一個5－或6－員雜環與另一個飽和、不飽和或芳香系碳環稠合，例如：苯、己環、環己烯或環己二烯環，或與另一個5－或6－員雜環稠合(其中後者同樣可為飽和、不飽和或芳香系)之雙環狀雜環。Or comprising a 5- or 6-membered heterocyclic ring as described above fused to another saturated, unsaturated or aromatic carbocyclic ring, for example: benzene, hexacyclo, cyclohexene or cyclohexadiene ring, or with another 5 - or a bicyclic heterocyclic ring in which a 6-membered heterocyclic ring is fused (wherein the latter may also be saturated, unsaturated or aromatic).

如上述雜環中之硫原子可氧化成S＝O或S(＝O)2 。The sulfur atom in the above heterocyclic ring can be oxidized to S=O or S(=O) 2 .

因此，雜芳基(hetearyl或heteroaryl)為具有1、2、3或4個選自氧、硫與氮所組成群中相同或相異雜原子作為環組員之5－或6－員雜芳香基，其可利用碳或氮附接且可再與苯環稠合，或5－至6－員雜芳香環可形成雙環系。雜芳基實例為利用碳附接如上述5－與6－員雜芳香環、利用氮附接之如上述5－員雜芳香環與雙環狀雜芳香基如：喹啉基、異喹啉基、喹唑啉基、喹啉基、吲哚基、苯并噻吩基、苯并呋喃基、苯并唑基、苯并噻唑基、苯并咪唑基、苯并吡唑基、苯并***基、吲哚基、1,2,4－***并[1,5－a]嘧啶基、1,2,4－***并[4,3－a]吡啶基、吡唑并[3,4－b]吡啶基、1,2,4－***并[1,5－a]吡啶基、咪唑并[1,2－a]吡啶基、咪唑并[3,4－a]嘧啶基，等等。Thus, a heteroaryl or heteroaryl is a 5- or 6-membered heteroaryl having 1, 2, 3 or 4 hetero-atoms selected from the group consisting of oxygen, sulfur and nitrogen as a ring member. It may be attached with carbon or nitrogen and may be fused to the benzene ring, or a 5- to 6-membered heteroaromatic ring may form a bicyclic ring system. Examples of the heteroaryl group are a 5-membered heteroaromatic ring and a bicyclic heteroaromatic group such as a quinolinyl group or an isoquinoline as described above, which are attached by a carbon such as the above 5- and 6-membered heteroaromatic ring. Base, quinazolinyl, quin Polinyl, fluorenyl, benzothienyl, benzofuranyl, benzo Azolyl, benzothiazolyl, benzimidazolyl, benzopyrazolyl, benzotriazolyl, anthracene 1,1,2,4-triazolo[1,5-a]pyrimidinyl, 1,2,4-triazolo[4,3-a]pyridyl, pyrazolo[3,4-b] Pyridyl, 1,2,4-triazolo[1,5-a]pyridyl, imidazo[1,2-a]pyridyl, imidazo[3,4-a]pyrimidinyl, and the like.

芳基：具有6至14個環組員之單環或多環芳香系碳環，例如：單環或雙環或單環至三環芳香系碳環，如，例如：苯基、萘基或蒽基。Aryl: a monocyclic or polycyclic aromatic carbocyclic ring having 6 to 14 ring members, for example, a monocyclic or bicyclic or monocyclic to tricyclic aromatic carbocyclic ring such as, for example, phenyl, naphthyl or anthracenyl. .

芳基烷基：利用伸烷基，特定言之亞甲基、1,1－伸乙基或1,2－伸乙基附接之芳基，例如：苯甲基、1－苯基乙基與2－苯基乙基。Arylalkyl: using an alkylene group, specifically a methylene group, a 1,1-extended ethyl group or a 1,2-extended ethyl group-attached aryl group, for example, a benzyl group, a 1-phenylethyl group With 2-phenylethyl.

雜環基烷基與雜芳基烷基：利用伸烷基，特定言之亞甲基、1,1－伸乙基或1,2－伸乙基附接之雜環基或雜芳基。Heterocyclylalkyl and heteroarylalkyl: using an alkylene group, specifically a methylene group, a 1,1-extended ethyl group or a 1,2-extended ethyl group-attached heterocyclic group or heteroaryl group.

特定具體實施例中，式I化合物中之代號定義如下－包括其本身及其相互組合－其已成為式I化合物之特定具體實施例：R1 為氫、胺基、氰基、C1 －C6 －烷基、C3 －C6 －烯基、C3 －C6 －炔基、苯基－(C1 －C6 )－烷基、雜環基－(C1 －C6 )－烷基或COR21 ，其中R21 如上述定義，特定言之C1 －C6 －烷基、C1 －C6 －烷氧基、苯基、苯基胺基或雜環基；其中取代基之如上述脂系、環狀或芳香系部份基團可部份或完全鹵化。特別佳者，R1 之定義為氫或C1 －C6 －烷基，特定言之甲基。In a particular embodiment, the symbols in the compounds of formula I are defined below - including themselves and their mutual combination - which have become specific embodiments of the compounds of formula I: R 1 is hydrogen, amine, cyano, C 1 -C 6 -alkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl, phenyl-(C 1 -C 6 )-alkyl, heterocyclyl-(C 1 -C 6 )-alkane Or COR 21 , wherein R 21 is as defined above, specifically C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, phenyl, phenylamino or heterocyclic; wherein the substituent The above aliphatic, cyclic or aromatic moiety may be partially or completely halogenated. Particularly preferred, R 1 is defined as hydrogen or C 1 -C 6 -alkyl, in particular methyl.

R2 為胺基、氰基、C1 －C6 －烷基、C3 －C6 －烯基、C3 －C6 －炔基、苯基－(C1 －C6 )－烷基、雜環基－(C1 －C6 )－烷基或COR21 ，其中R21 如上述定義，特定言之C1 －C6 －烷基、C1 －C6 －烷氧基、苯基、苯基胺基或雜環基；其中取代基之如上述脂系、環狀或芳香系部份基團可部份或完全鹵化。特別佳者，R2 之定義為C1 －C6 －烷基，特定言之甲基。R 2 is an amino group, a cyano group, a C 1 -C 6 -alkyl group, a C 3 -C 6 -alkenyl group, a C 3 -C 6 -alkynyl group, a phenyl-(C 1 -C 6 )-alkyl group, Heterocyclyl-(C 1 -C 6 )-alkyl or COR 21 , wherein R 21 is as defined above, specifically C 1 -C 6 -alkyl, C 1 -C 6 -alkoxy, phenyl, A phenylamino group or a heterocyclic group; wherein the substituent such as the above aliphatic, cyclic or aromatic moiety may be partially or completely halogenated. Particularly preferred, R 2 is defined as C 1 -C 6 -alkyl, specifically methyl.

R3 為氫、鹵素、C1 －C6 －烷基或鹵－C1 －C6 －烷基。R 3 is hydrogen, halogen, C 1 -C 6 -alkyl or halo-C 1 -C 6 -alkyl.

R4 、R5 與/或R6 為氫。R 4 , R 5 and/or R 6 are hydrogen.

A1 為選自下列各物所組成群中之芳基或雜芳基：苯基、萘基、呋喃基、噻吩基、吡咯基、吡唑基、噻唑基、異噻唑基、唑基、異唑基、***基、四唑基、吡啶基、嗒基、嘧啶基、吡基、三基或四基。特定言之，A1 為選自下列各物所組成群中：苯基、呋喃基、噻吩基、***基、四唑基或吡啶基。特別佳者，A1 之定義為苯基或吡啶基，特定言之苯基。A 1 is an aryl or heteroaryl group selected from the group consisting of phenyl, naphthyl, furyl, thienyl, pyrrolyl, pyrazolyl, thiazolyl, isothiazolyl, Azolyl, different Azyl, triazolyl, tetrazolyl, pyridyl, anthracene Base, pyrimidinyl, pyridyl Base, three Base or four base. Specifically, A 1 is selected from the group consisting of phenyl, furyl, thienyl, triazolyl, tetrazolyl or pyridyl. Particularly preferred, A 1 is defined as phenyl or pyridyl, in particular phenyl.

另一項較佳具體實施例中，A1 為雙環系芳香基，特定言之萘基或如上述雙環系雜芳香基中之一，如：喹啉基、異喹啉基、喹唑啉基、喹啉基、吲哚基、苯并噻吩基、苯并呋喃基、苯并唑基、苯并噻唑基、苯并咪唑基、苯并吡唑基、苯并***、吲哚基、1,2,4－***并[1,5－a]嘧啶基、1,2,4－***并[4,3－a]吡啶基、吡唑并[3,4－b]吡啶基、1,2,4－***并[1,5－a]吡啶基、咪唑并[1,2－a]吡啶基、咪唑并[3,4－a]嘧啶基，尤指吲哚基，極特別指3－吲哚基。In another preferred embodiment, A 1 is a bicyclic aromatic group, specifically a naphthyl group or one of the above bicyclic heteroaryl groups, such as a quinolyl group, an isoquinolyl group, or a quinazolinyl group. Quino Polinyl, fluorenyl, benzothienyl, benzofuranyl, benzo Azolyl, benzothiazolyl, benzimidazolyl, benzopyrazolyl, benzotriazole, anthracene 1,1,2,4-triazolo[1,5-a]pyrimidinyl, 1,2,4-triazolo[4,3-a]pyridyl, pyrazolo[3,4-b] Pyridyl, 1,2,4-triazolo[1,5-a]pyridyl, imidazo[1,2-a]pyridyl, imidazo[3,4-a]pyrimidinyl, especially 吲哚Base, especially especially 3-mercapto.

A2 為選自下列各物所組成群中之芳基或雜芳基：苯基、萘基、呋喃基、噻吩基、吡咯基、吡唑基、噻唑基、異噻唑基、唑基、異唑基、***基、四唑基、吡啶基、嗒基、嘧啶基、吡基、三基或四基，特定言之選自下列各物所組成群中：苯基、呋喃基、噻吩基、***基、四唑基或吡啶基。特別佳者，A2 之定義為苯基或噻吩基，特定言之苯基。A 2 is an aryl or heteroaryl group selected from the group consisting of phenyl, naphthyl, furyl, thienyl, pyrrolyl, pyrazolyl, thiazolyl, isothiazolyl, Azolyl, different Azyl, triazolyl, tetrazolyl, pyridyl, anthracene Base, pyrimidinyl, pyridyl Base, three Base or four The group, in particular, is selected from the group consisting of phenyl, furyl, thienyl, triazolyl, tetrazolyl or pyridyl. Particularly preferred, A 2 is defined as phenyl or thienyl, in particular phenyl.

根據本發明，A1 帶有氫以外之如上述基團Ra 。較佳者，此基團附接在A1 與氮之附接點之鄰位上，或特定言之在A1 之碳原子之鄰位上；此鄰位最好與A1 為單環或多環之芳香系或雜芳香系無關。According to the invention, A 1 carries a group R a other than hydrogen as described above. Preferably, the group is attached to the ortho position of the attachment point of A 1 to the nitrogen, or specifically to the ortho position of the carbon atom of A 1 ; this ortho position is preferably a single ring with A 1 or Polycyclic aromatic or heteroaromatic systems are not related.

本發明另一項較佳具體實施例中，若A1 為多環芳香系或雜芳香系環，基團Ra 最好不附接包含A1 附接點之多環系中之環，亦即利用附接環外雙鍵之A1 ，形成哌環(＝"聯結環")。具有三個或多個環之環系中，Ra 最好附接直接鄰接"聯結環"之環。特別佳者，Ra 儘可能接近A1 之附接點。此時，Ra 特別位在橋頭原子之α－位置，此位置最接近A1 與環外雙鍵之附接點。In another preferred embodiment of the present invention, if A 1 is a polycyclic aromatic or heteroaromatic ring, the group R a is preferably not attached to the ring in the polycyclic ring system containing the A 1 attachment point. That is, using A 1 attached to the outer double bond of the ring to form a pipe Ring (="connection ring"). In a ring system having three or more rings, R a is preferably attached directly to the ring of the "joint ring". Particularly good, R a is as close as possible to the attachment point of A 1 . At this time, R a is particularly located at the α-position of the bridgehead atom, which is closest to the attachment point of A 1 and the outer double bond.

若Ra 附接氮原子時，Ra 最好不為鹵素、C1 －C6 －烷基硫、C1 －C6 －烷基亞磺醯基、Z1 P(O)(OR9 )2 ，其中Z1 為一鍵結。本發明較佳具體實施例中，Ra 附接碳原子。If a nitrogen atom attached to R a, R a is preferably not halo, C 1 -C 6 - alkylthio, C 1 -C 6 - alkylsulfinyl acyl, Z 1 P (O) ( OR 9) 2 , wherein Z 1 is a bond. In a preferred embodiment of the invention, R a is attached to a carbon atom.

Ra 較佳為如下定義之一：－鹵素、氰基、硝基、C1 －C6 －烷基、C3 －C6 －環烷基、C2 －C6 －烯基、C2 －C6 －炔基、[三－(C1 －C6 )－烷基矽烷基]－(C2 －C6 )－炔基、C1 －C6 －烷基硫、C1 －C6 －烷基亞磺醯基、芳基、雜環基，特定言之5－或6－員雜環基，其中芳基與雜環基為未經取代或可帶有1或2個選自下列各物所組成群中之基團：C1 －C4 －烷基、C1 －C4 －鹵烷基、C1 －C4 －烷氧基、C1 －C4 －鹵烷氧基、CN與鹵素；－Z1 P(O)(OR9 )2 ，其中Z1 為一鍵結或－CH2 －，R9 分別為氫或C1 －C6 －烷基；－Z3 COR11 ，其中Z3 為一鍵結與R11 如上述定義，特定言之為氫、C1－C6－烷基、羥基、C1－C6－烷氧基、C3－C6－烯基氧、C3－C6－炔基氧、胺基、C1－C6－烷基胺基、[二－(C1－C6)－烷基]胺基、C1－C6－烷氧基胺基、N－C1－C6－烷氧基－N－C1－C6－烷基胺基、[二－(C1－C6)－烷氧基]胺基、C1－C6－烷基磺醯基胺基、C1－C6－烷基胺基磺醯基胺基、[二－(C1－C6)－烷基胺基]磺醯基胺基、苯基、苯氧基、苯基胺基、萘基或雜環基，尤指利用碳附接之5－或6－員雜芳基；－Z4 NR12 R13 ，其中Z4 為一鍵結或－CH2 －，R12 與R13 如上述定義，特定言之分別獨立為氫、C1－C6－烷基、C3－C6－環烷基、C3－C6－烯基、C3－C6－炔基、C1－C6－烷基羰基、[二－(C1－C6)－烷基胺基]羰基、C1－C6－烷氧基羰基、C1－C6－烷基磺醯基、C1－C6－烷基胺基磺醯基、[二－(C1－C6)－烷基胺基]磺醯基、C3－C6－環烷基羰基、苯基羰基、苯基胺基羰基、苯基磺醯基、苯基磺醯基胺基羰基或雜環基羰基，尤指利用碳附接之5－或6－員雜芳基羰基；－Z5 CH＝N－O－R14 ，其中Z5 為一鍵結，R14 為氫或C1 －C6 －烷基；或－Z6 OR15 ，其中Z6 為一鍵結或－CH2 －，R15 如上述定義，特定言之為C3－C6－環烷基、C3－C6－烯基、C3－C6－炔基、C1－C6－烷基羰基、C1－C6－烷氧基羰基－(C1－C6)－烷基、二－(C1－C6－烷氧基羰基)－C1－C6－烷基、苯基羰基或苯基，R15亦可為氫、C1－C6－烷基或苯基－C1－C6－烷基；或－Z7 SO2 R16 ，其中Z7 為一鍵結或CH2 ，R16 為C1 －C6 －烷基或苯基；且其中Ra 之取代基之如上述脂系、環狀或芳香系部份基團可部份或完全鹵化。R a is preferably one of the following definitions: - halogen, cyano, nitro, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 2 -C 6 -alkenyl, C 2 - C 6 -alkynyl, [tri-(C 1 -C 6 )-alkyldecyl]-(C 2 -C 6 )-alkynyl, C 1 -C 6 -alkylthio, C 1 -C 6 - An alkylsulfinyl group, an aryl group, a heterocyclic group, specifically a 5- or 6-membered heterocyclic group, wherein the aryl group and the heterocyclic group are unsubstituted or may have 1 or 2 selected from the following a group in the group consisting of: C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkoxy, CN And halogen; -Z 1 P(O)(OR 9 ) 2 , wherein Z 1 is a bond or -CH 2 -, R 9 is hydrogen or C 1 -C 6 -alkyl, respectively; -Z 3 COR 11 , Wherein Z 3 is a bond and R 11 is as defined above, specifically hydrogen, C1-C6-alkyl, hydroxy, C1-C6-alkoxy, C3-C6-alkenyloxy, C3-C6-alkyne Oxygen, amine, C1-C6-alkylamino, [di-(C1-C6)-alkyl]amino, C1-C6-alkoxyamino, N-C1-C6-alkoxy- N-C1-C6-alkylamine group, [Di-(C1-C6)-alkoxy]amino, C1-C6-alkylsulfonylamino, C1-C6-alkylaminosulfonylamino, [di-(C1-C6) -alkylamino]sulfonylamino, phenyl, phenoxy, phenylamino, naphthyl or heterocyclic, especially 5- or 6-membered heteroaryl attached by carbon; -Z 4 NR 12 R 13 , wherein Z 4 is a bond or -CH 2 -, and R 12 and R 13 are as defined above, and are specifically independently hydrogen, C1-C6-alkyl, C3-C6-cycloalkyl , C3-C6-alkenyl, C3-C6-alkynyl, C1-C6-alkylcarbonyl, [di-(C1-C6)-alkylamino]carbonyl, C1-C6-alkoxycarbonyl, C1- C6-alkylsulfonyl, C1-C6-alkylaminosulfonyl, [di-(C1-C6)-alkylamino]sulfonyl, C3-C6-cycloalkylcarbonyl, phenylcarbonyl , phenylaminocarbonyl, phenylsulfonyl, phenylsulfonylaminocarbonyl or heterocyclylcarbonyl, especially 5- or 6-membered heteroarylcarbonyl bonded with carbon; -Z 5 CH= N-O-R 14 , wherein Z 5 is a bond, R 14 is hydrogen or C 1 -C 6 -alkyl; or -Z 6 OR 15 , wherein Z 6 is a bond or -CH 2 -, R 15 is as defined above, specifically C3-C6-cycloalkyl, C3-C6-alkenyl, C3-C6-alkynyl, C1-C6-alkylcarbonyl, C1-C6-alkoxycarbonyl-( C1-C6)-alkyl, bis-(C1-C6-alkoxycarbonyl)-C1-C6-alkyl, phenylcarbonyl or phenyl, R15 may also be hydrogen, C1-C6-alkyl or phenyl -C1-C6-alkyl; or -Z 7 SO 2 R 16 , wherein Z 7 is a bond or CH 2 , R 16 is C 1 -C 6 -alkyl or phenyl; and wherein R a substituent The above aliphatic, cyclic or aromatic moiety may be partially or completely halogenated.

若Ra 附接氮原子時，Ra 最好不為鹵素、C1 －C6 －烷基硫、C1 －C6 －烷基亞磺醯基、Z1 P(O)(OR9 )2 ，其中Z1 為一鍵結。本發明較佳具體實施例中，Ra 附接碳原子。If a nitrogen atom attached to R a, R a is preferably not halo, C 1 -C 6 - alkylthio, C 1 -C 6 - alkylsulfinyl acyl, Z 1 P (O) ( OR 9) 2 , wherein Z 1 is a bond. In a preferred embodiment of the invention, R a is attached to a carbon atom.

Ra 特定言之如下定義之一：－鹵素、氰基、硝基、C1 －C6 －烷基硫、C1 －C6 －烷基亞磺醯基、芳基、雜環基，其中最後兩個基團為未經取代或可帶有1或2個選自下列各物所組成群中之基團：C1 －C4 －烷基、C1 －C4 －鹵烷基、C1 －C4 －烷氧基、C1 －C4 －鹵烷氧基、CN與鹵素；－C2 －C6 －烯基、C2 －C6 －炔基，－Z1 P(O)(OR9 )2 ，其中Z1 為一鍵結或－CH2 －，且基團R9 分別為氫或C1 －C6 －烷基；或－Z3 COR11 ，其中Z3 為一鍵結與R11 為氫、C1 －C6 －烷基、羥基、C1 －C6 －烷氧基、C3 －C6 －烯基氧、C3 －C6 －炔基氧、胺基、C1 －C6 －烷基胺基、[二－(C1 －C6 )－烷基]胺基、C1 －C6 －烷氧基胺基、N－C1 －C6 －烷氧基－N－C1 －C6 －烷基胺基、C1 －C6 －烷基磺醯基胺基、C1 －C6 －烷基胺基磺醯基胺基、[二－(C1 －C6 )－烷基胺基]磺醯基胺基、苯基、苯氧基、苯基胺基、萘基或雜環基，尤指利用碳附接之5－或6－員雜芳基；或－Z4 NR12 R13 ，其中Z4 為一鍵結或－CH2 －，R12 與R13 分別獨立為氫、C1 －C6 －烷基、C3 －C6 －環烷基、C3 －C6 －烯基、C3 －C6 －炔基、C1 －C6 －烷基羰基、[二－(C1 －C6 )－烷基胺基]羰基、C1 －C6 －烷氧基羰基、C1 －C6 －烷基磺醯基、苯基羰基、苯基磺醯基或雜環基羰基，尤指利用碳附接之5－或6－員雜芳基羰基；或－Z5 CH＝N－O－R14 ，其中Z5 為一鍵結與R14 為氫或C1 －C6 －烷基；或－Z6 OR15 ，其中Z6 為一鍵結或－CH2 －與R15 為氫、C1 －C6 －烷基、C3 －C6 －環烷基、C3 －C6 －烯基、C3 －C6 －炔基、C1 －C6 －烷基羰基、C1 －C6 －烷氧基羰基－(C1 －C6 )－烷基、苯基或苯基－(C1 －C6 )－烷基；或－Z7 SO2 R16 ，其中Z7 為一鍵結或CH2 與R16 為C1 －C6 －烷基或苯基；且其中Ra 之取代基之如上述脂系、環狀或芳香系部份基團可部份或完全鹵化。R a specific definition of one of the following words: - halogen, cyano, nitro, C 1 -C 6 - alkylthio, C 1 -C 6 - alkylsulfinyl acyl group, an aryl group, a heterocyclic group, wherein The last two groups are unsubstituted or may carry 1 or 2 groups selected from the group consisting of C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 1- C 4 -alkoxy, C 1 -C 4 -haloalkoxy, CN and halogen; -C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, -Z 1 P(O) (OR 9 ) 2 , wherein Z 1 is a bond or —CH 2 —, and the group R 9 is independently hydrogen or C 1 -C 6 -alkyl; or -Z 3 COR 11 , wherein Z 3 is a bond And R 11 is hydrogen, C 1 -C 6 -alkyl, hydroxy, C 1 -C 6 -alkoxy, C 3 -C 6 -alkenyloxy, C 3 -C 6 -alkynyloxy,amino , C 1 -C 6 -alkylamino, [di-(C 1 -C 6 )-alkyl]amino, C 1 -C 6 -alkoxyamino, N-C 1 -C 6 -alkane Oxy-N-C 1 -C 6 -alkylamino, C 1 -C 6 -alkylsulfonylamino, C 1 -C 6 -alkylaminosulfonylamino, [di-( C 1 -C 6 )-alkylamino]sulfonylamine a phenyl, phenoxy, phenylamino, naphthyl or heterocyclic group, especially a 5- or 6-membered heteroaryl group attached using carbon; or -Z 4 NR 12 R 13 wherein Z 4 Is a bond or -CH 2 -, R 12 and R 13 are each independently hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl, C 1 -C 6 -alkylcarbonyl, [di-(C 1 -C 6 )-alkylamino]carbonyl, C 1 -C 6 -alkoxycarbonyl, C 1 -C 6 -alkylsulfonyl, phenylcarbonyl, phenylsulfonyl or heterocyclic carbonyl, especially 5- or 6-membered heteroarylcarbonyl bonded with carbon; or -Z 5 CH=N-O -R 14 , wherein Z 5 is a bond and R 14 is hydrogen or C 1 -C 6 -alkyl; or -Z 6 OR 15 , wherein Z 6 is a bond or -CH 2 - and R 15 is hydrogen , C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl, C 1 -C 6 -alkylcarbonyl, C 1 -C 6 -alkoxycarbonyl-(C 1 -C 6 )-alkyl, phenyl or phenyl-(C 1 -C 6 )-alkyl; or -Z 7 SO 2 R 16 wherein Z 7 is One bond or CH 2 and R 16 are C 1 - C 6 -alkyl or phenyl; and wherein the substituent of R a such as the above aliphatic, cyclic or aromatic moiety may be partially or completely halogenated.

尤其佳為Ra 為選自下列各物所組成群中之基團：鹵素、氰基、硝基、C2 －C4 －烯基與C2 －C4 －炔基、NH－C(O)－C1 －C6 －烷基、NH－S(O)2 －C1 －C6 －烷基與5－員雜芳基，例如：唑基、噻唑基、異唑基、異噻唑基，其中如上述雜芳基可帶有1或2個選自下列各物所組成群中之基團：C1 －C2 －烷基、C1 －C2 －鹵烷基與鹵素，且特定言之其位在A1 之鄰位之一。Particularly preferably, R a is a group selected from the group consisting of halogen, cyano, nitro, C 2 -C 4 -alkenyl and C 2 -C 4 -alkynyl, NH-C(O )-C 1 -C 6 -alkyl, NH-S(O) 2 -C 1 -C 6 -alkyl and 5-membered heteroaryl, for example: Azolyl, thiazolyl, iso An azolyl, isothiazolyl group, wherein the heteroaryl group as described above may have 1 or 2 groups selected from the group consisting of C 1 -C 2 -alkyl, C 1 -C 2 -halane The base is halogen and, in particular, is in one of the ortho positions of A 1 .

Rb 、Rc 、Rd 、Re 與Rf 特定言之為氫，或分別獨立具有Ra 所述及之較佳或特別佳之定義。R b , R c , R d , R e and R f are specifically hydrogen, or each independently has a preferred or particularly preferred definition as described for R a .

特定言之，基團Rb 、Rc 、Rd 、Re 與Rf 分別獨立選自下列各物所組成群中：氫、鹵素、C1 －C4 －烷基、C2 －C4 －烯基、C2 －C4 －炔基、C1 －C4 －烷氧基、C1 －C4 －鹵烷基與C1 －C4 －鹵烷氧基，其中Rb 、Rc 、Rd 、Re 或Rf 中兩個附接在A1 或A2 兩個相鄰個碳原子上之基團可形成基團O－CH2 －O。In particular, the groups R b , R c , R d , R e and R f are each independently selected from the group consisting of hydrogen, halogen, C 1 -C 4 -alkyl, C 2 -C 4 Alkenyl, C 2 -C 4 -alkynyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkyl and C 1 -C 4 -haloalkoxy, wherein R b , R c Two of R d , R e or R f attached to two adjacent carbon atoms of A 1 or A 2 may form a group O-CH 2 —O.

特定言之，Rb 為不同於氫之基團。R1 較佳為位於A1 鄰位之基團，亦即若Ra 亦位於鄰位，則Rb 位於第二個鄰位。In particular, R b is a group different from hydrogen. R 1 is preferably a group located ortho to A 1 , that is, if R a is also in the ortho position, R b is in the second ortho position.

若基團Rb 、Rc 中1或2個為氫以外之取代基時，其可特別選自如上述較佳取代基中，尤其選自下列各物所組成群中：鹵素、C1 －C4 －烷基、C1 －C4 －烷氧基、C1 －C4 －鹵烷基、C2 －C4 －烯基、C2 －C4 －炔基與C1 －C4 －鹵烷氧基，或Rb 與Rc 共同為基團O－CH2 －O。If one or two of the radicals R b and R c are substituents other than hydrogen, they may be selected in particular from the preferred substituents described above, in particular from the group consisting of halogens, C 1 -C 4 -alkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -haloalkyl, C 2 -C 4 -alkenyl, C 2 -C 4 -alkynyl and C 1 -C 4 -halide Alkoxy, or R b and R c together are a group O-CH 2 -O.

A2 特定言之為未經取代，或Rd 、Re 與Rf 中1或2個取代基為氫以外之取代基。若取代基Rd 、Re 與Rf 中1或2個不為氫時，其可特別選自下列各物所組成群中：鹵素、C1 －C4 －烷基、C1 －C4 －烷氧基、C1 －C4 －鹵烷基與C1 －C4 －鹵烷氧基。A 2 is specifically unsubstituted, or one or two substituents of R d , R e and R f are substituents other than hydrogen. If 1 or 2 of the substituents R d , R e and R f are not hydrogen, they may be selected in particular from the group consisting of halogen, C 1 -C 4 -alkyl, C 1 -C 4 An alkoxy group, a C 1 -C 4 -haloalkyl group and a C 1 -C 4 -haloalkoxy group.

本發明內容中取代基定義完全與本發明內容中其他取代基之定義獨立。然而，特別佳之式I化合物為其中多數或所有代號均為較佳或特別佳之定義。The definition of a substituent in the context of the present invention is completely independent of the definition of the other substituents in the context of the present invention. However, particularly preferred compounds of formula I are those in which most or all of the symbols are preferred or particularly preferred.

此外，已發現哌環上之環外雙鍵宜為Z－構形，亦即基團A1 (Ra Rb Rc )與帶有基團R2 之環氮相對於此雙鍵呈順式。因此本發明較佳具體實施例係有關式(Z) －I哌化合物，其中代號A1 、A2 、R1 －R6 與Ra －Rf 如上述定義，亦有關Z－異構物(Z) －I與式(E) －I之E－異構物之混合物，其中E/Z比例為<1：1，特定言之<1：2，特別佳為<1：4，尤其佳為<1：10。式(E) －I中，代號A1 、A2 、R1 －R6 與Ra －Rf 亦如上述定義。In addition, it has been found that The extra-ring double bond on the ring is preferably in the Z-configuration, i.e., the group A 1 (R a R b R c ) and the ring nitrogen bearing the group R 2 are cis relative to the double bond. Therefore, a preferred embodiment of the invention is related to formula (Z) -I a compound wherein the codes A 1 , A 2 , R 1 -R 6 and R a -R f are as defined above, and also relates to the Z-isomer (Z) -I and the E-isomer of formula (E) -I A mixture wherein the E/Z ratio is < 1:1, specifically <1:2, particularly preferably <1:4, especially preferably <1:10. In the formula (E) -I, the symbols A 1 , A 2 , R 1 - R 6 and R a - R f are also as defined above.

此外，已發現帶有R4 之碳原子呈S－組態。因此本發明較佳具體實施例係有關式I－S哌化合物，其中代號A1 、A2 、R1 －R6 與Ra －Rf 如上述定義，亦有關S－對映異構物(S) －I與式(R) －I之R－對映異構物之混合物，其中R/S比例為<1：1，特定言之<1：2，特別佳為<1：4，尤指<1：10。式(R) －I中代號A1 、A2 、R1 －R6 與Ra －Rf 亦如上述定義。Furthermore, it has been found that the carbon atom with R 4 is in the S-configuration. Therefore, a preferred embodiment of the invention is related to formula I-S. a compound wherein the codes A 1 , A 2 , R 1 -R 6 and R a -R f are as defined above, and also relates to the S-enantiomer (S) -I and the R-pair of formula (R) -I A mixture of enantiomers wherein the R/S ratio is < 1:1, specifically <1:2, particularly preferably <1:4, especially <1:10. The codes A 1 , A 2 , R 1 - R 6 and R a - R f in the formula (R) -I are also as defined above.

特定言之，較佳式I化合物為其中兩個環外雙鍵均呈Z－構形，而帶有R4 之碳原子則呈S－組態。下文中，此等化合物亦稱為化合物(Z,S) －I。Specific words, preferred compounds of formula I wherein two exocyclic double bond showed Z- configuration, and the carbon bearing R 4 S- shape configuration of the atoms. Hereinafter, these compounds are also referred to as compounds (Z, S) -I.

特定言之，較佳為式I.1化合物，其中R1 、R3 、R4 、R5 與R6 為氫，R2 為CH3 ，特別佳為化合物(Z ,S )－I.1，其在指定之(1)與(2)位置上呈Z －或S －組態。較佳化合物I.1與(Z ,S )－I.1之實例為彼等其中A1 、Ra 、Rb 與Rc 如表1中定義者： In particular, a compound of the formula I.1, wherein R 1 , R 3 , R 4 , R 5 and R 6 are hydrogen and R 2 is CH 3 , particularly preferably the compound ( Z , S )-I.1 It is Z- or S -configured at the specified (1) and (2) positions. Examples of preferred compounds I.1 and ( Z , S )-I.1 are those wherein A 1 , R a , R b and R c are as defined in Table 1:

下列化合物I.1.1至I.1－3434本身即為本發明較佳具體實施例。The following compounds I.1.1 to I.1-3434 are themselves preferred embodiments of the invention.

同樣較佳為式I.2化合物，特別佳為化合物I.2.1－I.2.3434，特定言之化合物(Z,S )－I.2.1－I.2.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S )－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氯苯基。Also preferred are the compounds of the formula I.2, particularly preferably the compounds I.2.1 to I.2.3434, in particular the compounds ( Z,S )-I.2.1-I.2.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or ( Z,S )-I.1.1-I.1.3434 where A 2 R d R e R f is 2-chlorophenyl.

同樣較佳為式I.3化合物，特別佳為化合物I.3.1－I.3.3434，特定言之化合物(Z,S )－I.3.1－I.3.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－氯苯基。Also preferred are the compounds of the formula I.3, particularly preferably the compounds I.3.1-I.3.3434, in particular the compounds ( Z,S )-I.3.1-I.3.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z, S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-chlorophenyl.

同樣較佳為式I.4化合物，特別佳為化合物I.4.1－I.4.3434，特定言之化合物(Z,S )－I.4.1－I.4.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－氯苯基。Also preferred are the compounds of the formula I.4, particularly preferably the compounds I.4.1 to I.4.3434, in particular the compounds ( Z,S )-I.4.1-I.4.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-chlorophenyl.

同樣較佳為式I.5化合物，特別佳為化合物I.5.1－I.5.3434，特定言之化合物(Z,S )－I.5.1－I.5.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－三氟甲基苯基。Also preferred are the compounds of the formula I.5, particularly preferably the compounds I.5.1-I.5.3434, in particular the compounds ( Z,S )-I.5.1-I.5.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-trifluoromethylphenyl.

同樣較佳為式I.6化合物，特別佳為化合物I.6.1－I.6.3434，特定言之化合物(Z,S )－I.6.1－I.6.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－三氟甲基苯基。Also preferred are the compounds of the formula I.6, particularly preferably the compounds I.6.1-I.6.3434, in particular the compounds ( Z,S )-I.6.1-I.6.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z, S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-trifluoromethylphenyl.

同樣較佳為式I.7化合物，特別佳為化合物I.7.1－I.7.3434，特定言之化合物(Z,S )－I.7.1－I.7.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－三氟甲基苯基。Also preferred are the compounds of the formula I.7, particularly preferably the compounds I.7.1-I.7.3434, in particular the compounds ( Z,S )-I.7.1-I.7.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z, S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-trifluoromethylphenyl.

同樣較佳為式I.8化合物，特別佳為化合物I.8.1－I.8.3434，特定言之化合物(Z,S )－I.8.1－I.8.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－甲氧基苯基。Also preferred are the compounds of the formula I.8, particularly preferably the compounds I.8.1-I.8.3434, in particular the compounds ( Z,S )-I.8.1-I.8.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-methoxyphenyl.

同樣較佳為式I.9化合物，特別佳為化合物I.9.1－I.9.3434，特定言之化合物(Z,S )－I.9.1－I.9.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－甲氧基苯基。Also preferred are the compounds of the formula I.9, particularly preferably the compounds I.9.1-I.9.3434, in particular the compounds ( Z,S )-I.9.1-I.9.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z, S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-methoxyphenyl.

同樣較佳為式I.10化合物，特別佳為化合物I.10.1－I.10.3434，特定言之化合物(Z,S )－I.10.1－I.10.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－甲氧基苯基。Also preferred are the compounds of the formula I.10, particularly preferably the compounds I.10.1 to I.10.3434, in particular the compounds ( Z,S )-I.10.1-I.10.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-methoxyphenyl.

同樣較佳為式I.11化合物，特別佳為化合物I.11.1－I.11.3434，特定言之化合物(Z,S )－I.11.1－I.11.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氟苯基。Also preferred are the compounds of the formula I.11, particularly preferably the compounds I.11.1-I.11.3434, in particular the compounds ( Z,S )-I.11.1-I.11.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z, S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-fluorophenyl.

同樣較佳為式I.12化合物，特別佳為化合物I.12.1－I.12.3434，特定言之化合物(Z,S )－I.12.1－I.12.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－氟苯基。Also preferred are the compounds of the formula I.12, particularly preferably the compounds I.12.1-I.12.3434, in particular the compounds ( Z,S )-I.12.1-I.12.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-fluorophenyl.

同樣較佳為式I.13化合物，特別佳為化合物I.13.1－I.13.3434，特定言之化合物(Z,S )－I.13.1－I.13.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－氟苯基。Also preferred are the compounds of the formula I.13, particularly preferably the compounds I.13.1-I.13.3434, in particular the compounds ( Z,S )-I.13.1-I.13.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z, S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-fluorophenyl.

同樣較佳為式I.14化合物，特別佳為化合物I.14.1－I.14.3434，特定言之化合物(Z,S )－I.14.1－I.14.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－甲基苯基。Also preferred are the compounds of the formula I.14, particularly preferably the compounds I.14.1-I.14.3434, in particular the compounds ( Z,S )-I.14.1-I.14.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-methylphenyl.

同樣較佳為式I.15化合物，特別佳為化合物I.15.1－I.15.3434，特定言之化合物(Z,S )－I.15.1－I.15.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－甲基苯基。Also preferred are the compounds of the formula I.15, particularly preferably the compounds I.15.1-I.15.3434, in particular the compounds ( Z,S )-I.15.1-I.15.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-methylphenyl.

同樣較佳為式I.16化合物，特別佳為化合物I.16.1－I.16.3434，特定言之化合物(Z,S )－I.16.1－I.16.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－甲基苯基。Also preferred are the compounds of the formula I.16, particularly preferably the compounds I.16.1-I.16.3434, in particular the compounds ( Z,S )-I.16.1-I.16.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z, S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-methylphenyl.

同樣較佳為式I.17化合物，特別佳為化合物I.17.1－I.17.3434，特定言之化合物(Z,S )－I.17.1－I.17.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氯－3－甲基苯基。Also preferred are the compounds of the formula I.17, particularly preferably the compounds I.17.1-I.17.3434, in particular the compounds ( Z,S )-I.17.1-I.17.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-chloro-3-methylphenyl.

同樣較佳為式I.18化合物，特別佳為化合物I.18.1－I.18.3434，特定言之化合物(Z,S )－I.18.1－I.18.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氯－4－甲基苯基。Also preferred are the compounds of the formula I.18, particularly preferably the compounds I.18.1-I.18.3434, in particular the compounds ( Z,S )-I.18.1-I.18.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-chloro-4-methylphenyl.

同樣較佳為式I.19化合物，特別佳為化合物I.19.1－I.19.3434，特定言之化合物(Z,S )－I.19.1－I.19.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氯－5－甲基苯基。Also preferred are the compounds of the formula I.19, particularly preferably the compounds I.19.1-I.19.3434, in particular the compounds ( Z,S )-I.19.1-I.19.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-chloro-5-methylphenyl.

同樣較佳為式I.20化合物，特別佳為化合物I.20.1－I.20.3434，特定言之化合物(Z,S )－I.20.1－I.20.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氯－6－甲基苯基。Also preferred are the compounds of the formula I.20, particularly preferably the compounds I.20.1-I.20.3434, in particular the compounds ( Z,S )-I.20.1-I.20.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-chloro-6-methylphenyl.

同樣較佳為式I.21化合物，特別佳為化合物I.21.1－I.21.3434，特定言之化合物(Z,S )－I.21.1－I.21.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2,3－二氯苯基。Also preferred are the compounds of the formula I.21, particularly preferably the compounds I.21.1-I.21.3434, in particular the compound ( Z,S )-I.21.1-I.21.3434, which differs from the corresponding compound I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2,3-dichlorophenyl.

同樣較佳為式I.22化合物，特別佳為化合物I.22.1－I.22.3434，特定言之化合物(Z,S )－I.22.1－I.22.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2,4－二氯苯基。Also preferred are the compounds of the formula I.22, particularly preferably the compounds I.22.1-I.22.3434, in particular the compounds ( Z,S )-I.22.1-I.22.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z, S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2,4-dichlorophenyl.

同樣較佳為式I.23化合物，特別佳為化合物I.23.1－I.23.3434，特定言之化合物(Z,S )－I.23.1－I.23.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2,5－二氯苯基。Also preferred are the compounds of the formula I.23, particularly preferably the compounds I.23.1-I.23.3434, in particular the compounds ( Z,S )-I.23.1-I.23.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z, S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2,5-dichlorophenyl.

同樣較佳為式I.24化合物，特別佳為化合物I.24.1－I.24.3434，特定言之化合物(Z,S )－I.24.1－I.24.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2,6－二氯苯基。Also preferred are the compounds of the formula I.24, particularly preferably the compounds I.24.1-I.24.3434, in particular the compounds ( Z,S )-I.24.1-I.24.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z, S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2,6-dichlorophenyl.

同樣較佳為式I.25化合物，特別佳為化合物I.25.1－I.25.3434，特定言之化合物(Z,S )－I.25.1－I.25.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氯－3－氟苯基。Also preferred are the compounds of the formula I.25, particularly preferably the compounds I.25.1-I.25.3434, in particular the compounds ( Z,S )-I.25.1-I.25.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-chloro-3-fluorophenyl.

同樣較佳為式I.26化合物，特別佳為化合物I.26.1－I.26.3434，特定言之化合物(Z,S )－I.26.1－I.26.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氯－4－氟苯基。Also preferred are the compounds of the formula I.26, particularly preferably the compounds I.26.1-I.26.3434, in particular the compounds ( Z,S )-I.26.1-I.26.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-chloro-4-fluorophenyl.

同樣較佳為式I.27化合物，特別佳為化合物I.27.1－I.27.3434，特定言之化合物(Z,S )－I.27.1－I.27.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氯－5－氟苯基。Also preferred are the compounds of the formula I.27, particularly preferably the compounds I.27.1-I.27.3434, in particular the compounds ( Z,S )-I.27.1-I.27.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z, S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-chloro-5-fluorophenyl.

同樣較佳為式I.28化合物，特別佳為化合物I.28.1－I.28.3434，特定言之化合物(Z,S )－I.28.1－I.28.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氯－6－氟苯基。Also preferred are the compounds of the formula I.28, particularly preferably the compounds I.28.1-I.28.3434, in particular the compounds ( Z,S )-I.28.1-I.28.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z, S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-chloro-6-fluorophenyl.

同樣較佳為式I.29化合物，特別佳為化合物I.29.l－I.29.3434，特定言之化合物(Z,S )－I.29.1－I.29.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2,3－二氟苯基。Also preferred are the compounds of the formula I.29, particularly preferably the compounds I.29.l-I.29.3434, in particular the compounds ( Z,S )-I.29.1-I.29.3434, which differ from the corresponding compounds I.1.1 -I.1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2,3-difluorophenyl.

同樣較佳為式I.30化合物，特別佳為化合物I.30.1－I.30.3434，特定言之化合物(Z,S )－I.30.1－I.30.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2,4－二氟苯基。Also preferred are the compounds of the formula I.30, particularly preferably the compounds I.30.1-I.30.3434, in particular the compounds ( Z,S )-I.30.1-I.30.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z, S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2,4-difluorophenyl.

同樣較佳為式I.31化合物，特別佳為化合物I.31.1－I.31.3434，特定言之化合物(Z,S )－I.31.1－I.31.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2,5－二氟苯基。Also preferred are the compounds of the formula I.31, particularly preferably the compounds I.31.1-I.31.3434, in particular the compounds ( Z,S )-I.31.1-I.31.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z, S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2,5-difluorophenyl.

同樣較佳為式I.32化合物，特別佳為化合物I.32.1－I.32.3434，特定言之化合物(Z,S )－I.32.1－I.32.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2,6－二氟苯基。Also preferred are the compounds of the formula I.32, particularly preferably the compounds I.32.1-I.32.3434, in particular the compounds ( Z,S )-I.32.1-I.32.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z, S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2,6-difluorophenyl.

同樣較佳為式I.33化合物，特別佳為化合物I.33.1－I.33.3434，特定言之化合物(Z,S )－I.33.1－I.33.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氟－3－氯苯基。Also preferred are the compounds of the formula I.33, particularly preferably the compounds I.33.1-I.33.3434, in particular the compounds ( Z,S )-I.33.1-I.33.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-fluoro-3-chlorophenyl.

同樣較佳為式I.34化合物，特別佳為化合物I.34.1－I.34.3434，特定言之化合物(Z,S )－I.34.1－I.34.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氟－4－氯苯基。Also preferred are the compounds of the formula I.34, particularly preferably the compounds I.34.1-I.34.3434, in particular the compounds ( Z,S )-I.34.1-I.34.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-fluoro-4-chlorophenyl.

同樣較佳為式I.35化合物，特別佳為化合物I.35.1－I.35.3434，特定言之化合物(Z,S )－I.35.1－I.35.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氟－5－氯苯基。Also preferred are the compounds of the formula I.35, particularly preferably the compounds I.35.1-I.35.3434, in particular the compounds ( Z,S )-I.35.1-I.35.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z, S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-fluoro-5-chlorophenyl.

同樣較佳為式I.36化合物，特別佳為化合物I.36.1－I.36.3434，特定言之化合物(Z,S )－I.36.1－I.36.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3,4－二氟苯基。Also preferred are the compounds of the formula I.36, particularly preferably the compounds I.36.1-I.36.3434, in particular the compounds ( Z,S )-I.36.1-I.36.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3,4-difluorophenyl.

同樣較佳為式I.37化合物，特別佳為化合物I.37.1－I.37.3434，特定言之化合物(Z,S )－I.37.1－I.37.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3,5－二氟苯基。Also preferred are the compounds of the formula I.37, particularly preferably the compounds I.37.1-I.37.3434, in particular the compounds ( Z,S )-I.37.1-I.37.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z, S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3,5-difluorophenyl.

同樣較佳為式I.38化合物，特別佳為化合物I.38.1－I.38.3434，特定言之化合物(Z,S )－I.38.1－I.38.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3,4－二氯苯基。Also preferred are the compounds of the formula I.38, particularly preferably the compounds I.38.1-I.38.3434, in particular the compounds ( Z,S )-I.38.1-I.38.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z, S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3,4-dichlorophenyl.

同樣較佳為式I.39化合物，特別佳為化合物I.39.1－I.39.3434，特定言之化合物(Z,S )－I.39.1－I.39.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3,5－二氯苯基。Also preferred are the compounds of the formula I.39, particularly preferably the compounds I.39.1-I.39.3434, in particular the compounds ( Z,S )-I.39.1-I.39.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z, S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3,5-dichlorophenyl.

同樣較佳為式I.40化合物，特別佳為化合物I.40.1－I.40.3434，特定言之化合物(Z,S )－I.40.1－I.40.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－氟，4－氯苯基。Also preferred are the compounds of the formula I.40, particularly preferably the compounds I.40.1 to I.40.3434, in particular the compounds ( Z,S )-I.40.1-I.40.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-fluoro, 4-chlorophenyl.

同樣較佳為式I.41化合物，特別佳為化合物I.41.1－I.41.3434，特定言之化合物(Z,S )－I.41.1－I.41.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－氟，3－氯苯基。Also preferred are the compounds of the formula I.41, particularly preferably the compounds I.41.1-I.41.3434, in particular the compounds ( Z,S )-I.41.1-I.41.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-fluoro, 3-chlorophenyl.

同樣較佳為式I.42化合物，特別佳為化合物I.42.1－I.42.3434，特定言之化合物(Z,S )－I.42.1－I.42.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－氟，5－氯苯基。Also preferred are the compounds of the formula I.42, particularly preferably the compounds I.42.1-I.42.3434, in particular the compounds ( Z,S )-I.42.1-I.42.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-fluoro, 5-chlorophenyl.

同樣較佳為式I.43化合物，特別佳為化合物I.43.1－I.43.3434，特定言之化合物(Z,S )－I.43.1－I.43.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為吡啶－2－基。Also preferred are the compounds of the formula I.43, particularly preferably the compounds I.43.1-I.43.3434, in particular the compounds ( Z,S )-I.43.1-I.43.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z, S)-I.1.1-I.1.3434 where A 2 R d R e R f is pyridin-2-yl.

同樣較佳為式I.44化合物，特別佳為化合物I.44.1－I.44.3434，特定言之化合物(Z,S )－I.44.1－I.44.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－氯吡啶－2－基。Also preferred are the compounds of the formula I.44, particularly preferably the compounds I.44.1-I.44.3434, in particular the compounds ( Z,S )-I.44.1-I.44.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-chloropyridin-2-yl.

同樣較佳為式I.45化合物，特別佳為化合物I.45.1－I.45.3434，特定言之化合物(Z,S )－I.45.1－I.45.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－氯吡啶－2－基。Also preferred are the compounds of the formula I.45, particularly preferably the compounds I.45.1-I.45.3434, in particular the compounds ( Z,S )-I.45.1-I.45.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-chloropyridin-2-yl.

同樣較佳為式I.46化合物，特別佳為化合物I.46.1－I.46.3434，特定言之化合物(Z,S )－I.46.1－I.46.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－氯吡啶－2－基。Also preferred are the compounds of the formula I.46, particularly preferably the compounds I.46.1-I.46.3434, in particular the compounds ( Z,S )-I.46.1-I.46.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-chloropyridin-2-yl.

同樣較佳為式I.47化合物，特別佳為化合物I.47.1－I.47.3434，特定言之化合物(Z,S )－I.47.1－I.47.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為6－氯吡啶－2－基。Also preferred are the compounds of the formula I.47, particularly preferably the compounds I.47.1-I.47.3434, in particular the compounds ( Z,S )-I.47.1-I.47.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 6-chloropyridin-2-yl.

同樣較佳為式I.48化合物，特別佳為化合物I.48.1－I.48.3434，特定言之化合物(Z,S )－I.48.1－I.48.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－三氟甲基吡啶－2－基。Also preferred are the compounds of the formula I.48, particularly preferably the compounds I.48.1-I.48.3434, in particular the compounds ( Z,S )-I.48.1-I.48.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-trifluoromethylpyridin-2-yl.

同樣較佳為式I.49化合物，特別佳為化合物I.49.1－I.49.3434，特定言之化合物(Z,S )－I.49.1－I.49.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－三氟甲基吡啶－2－基。Also preferred are the compounds of the formula I.49, particularly preferably the compounds I.49.1-I.49.3434, in particular the compounds ( Z,S )-I.49.1-I.49.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-trifluoromethylpyridin-2-yl.

同樣較佳為式I.50化合物，特別佳為化合物I.50.1－I.50.3434，特定言之化合物(Z,S )－I.50.1－I.50.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－三氟甲基吡啶－2－基。Also preferred are the compounds of the formula I.50, particularly preferably the compounds I.50.1-I.50.3434, in particular the compound ( Z,S )-I.50.1-I.50.3434, which differs from the corresponding compound I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-trifluoromethylpyridin-2-yl.

同樣較佳為式I.51化合物，特別佳為化合物I.51.1－I.51.3434，特定言之化合物(Z,S )－I.51.1－I.51.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為6－三氟甲基吡啶－2－基。Also preferred are the compounds of the formula I.51, particularly preferably the compounds I.51.1-I.51.3434, in particular the compounds ( Z,S )-I.51.1-I.51.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 6-trifluoromethylpyridin-2-yl.

同樣較佳為式I.52化合物，特別佳為化合物I.52.1－I.52.3434，特定言之化合物(Z,S )－I.52.1－I.52.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－甲氧基吡啶－2－基。Also preferred are the compounds of the formula I.52, particularly preferably the compounds I.52.1-I.52.3434, in particular the compounds ( Z,S )-I.52.1-I.52.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-methoxypyridin-2-yl.

同樣較佳為式I.53化合物，特別佳為化合物I.53.1－I.53.3434，特定言之化合物(Z,S )－I.53.1－I.53.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－甲氧基吡啶－2－基。Also preferred are the compounds of the formula I.53, particularly preferably the compounds I.53.1-I.53.3434, in particular the compounds ( Z,S )-I.53.1-I.53.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-methoxypyridin-2-yl.

同樣較佳為式I.54化合物，特別佳為化合物I.54.1－I.54.3434，特定言之化合物(Z,S )－I.54.1－I.54.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－甲氧基吡啶－2－基。Also preferred are the compounds of the formula I.54, particularly preferably the compounds I.54.1-I.54.3434, in particular the compounds ( Z,S )-I.54.1-I.54.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-methoxypyridin-2-yl.

同樣較佳為式I.55化合物，特別佳為化合物I.55.1－I.55.3434，特定言之化合物(Z,S )－I.55.1－I.55.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為6－甲氧基吡啶－2－基。Also preferred are the compounds of the formula I.55, particularly preferably the compounds I.55.1-I.55.3434, in particular the compounds ( Z,S )-I.55.1-I.55.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 6-methoxypyridin-2-yl.

同樣較佳為式I.56化合物，特別佳為化合物I.56.1－I.56.3434，特定言之化合物(Z,S )－I.56.1－I.56.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－氟吡啶－2－基。Also preferred are the compounds of the formula I.56, particularly preferably the compounds I.56.1-I.56.3434, in particular the compounds ( Z,S )-I.56.1-I.56.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z, S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-fluoropyridin-2-yl.

同樣較佳為式I.57化合物，特別佳為化合物I.57.1－I.57.3434，特定言之化合物(Z,S )－I.57.1－I.57.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－氟吡啶－2－基。Also preferred are the compounds of the formula I.57, particularly preferably the compounds I.57.1-I.57.3434, in particular the compounds ( Z,S )-I.57.1-I.57.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-fluoropyridin-2-yl.

同樣較佳為式I.58化合物，特別佳為化合物I.58.1－I.58.3434，特定言之化合物(Z,S )－I.58.1－I.58.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－氟吡啶－2－基。Also preferred are the compounds of the formula I.58, particularly preferably the compounds I.58.1-I.58.3434, in particular the compounds ( Z,S )-I.58.1-I.58.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-fluoropyridin-2-yl.

同樣較佳為式I.59化合物，特別佳為化合物I.59.1－I.59.3434，特定言之化合物(Z,S )－I.59.1－I.59.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為6－氟吡啶－2－基。Also preferred are the compounds of the formula I.59, particularly preferably the compounds I.59.1-I.59.3434, in particular the compounds ( Z,S )-I.59.1-I.59.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 6-fluoropyridin-2-yl.

同樣較佳為式I.60化合物，特別佳為化合物I.60.1－I.60.3434，特定言之化合物(Z,S )－I.60.1－I.60.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為吡啶－3－基。Also preferred are the compounds of the formula I.60, particularly preferably the compounds I.60.1-I.60.3434, in particular the compounds ( Z,S )-I.60.1-I.60.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is pyridin-3-yl.

同樣較佳為式I.61化合物，特別佳為化合物I.61.1－I.61.3434，特定言之化合物(Z,S )－I.61.1－I.61.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氯吡啶－3－基。Also preferred are the compounds of the formula I.61, particularly preferably the compounds I.61.1-I.61.3434, in particular the compounds ( Z,S )-I.61.1-I.61.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-chloropyridin-3-yl.

同樣較佳為式I.62化合物，特別佳為化合物I.62.1－I.62.3434，特定言之化合物(Z,S )－I.62.1－I.62.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－氯吡啶－3－基。Also preferred are the compounds of the formula I.62, particularly preferably the compounds I.62.1-I.62.3434, in particular the compounds ( Z,S )-I.62.1-I.62.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-chloropyridin-3-yl.

同樣較佳為式I.63化合物，特別佳為化合物I.63.1－I.63.3434，特定言之化合物(Z,S )－I.63.1－I.63.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－氯吡啶－3－基。Also preferred are the compounds of the formula I.63, particularly preferably the compounds I.63.1-I.63.3434, in particular the compounds ( Z,S )-I.63.1-I.63.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-chloropyridin-3-yl.

同樣較佳為式I.64化合物，特別佳為化合物I.64.1－I.64.3434，特定言之化合物(Z,S )－I.64.1－I.64.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為6－氯吡啶－3－基。Also preferred are the compounds of the formula I.64, particularly preferably the compounds I.64.1-I.64.3434, in particular the compounds ( Z,S )-I.64.1-I.64.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 6-chloropyridin-3-yl.

同樣較佳為式I.65化合物，特別佳為化合物I.65.1－I.65.3434，特定言之化合物(Z,S )－I.65.1－I.65.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－三氟甲基吡啶－3－基。Also preferred are the compounds of the formula I.65, particularly preferably the compounds I.65.1-I.65.3434, in particular the compounds ( Z,S )-I.65.1-I.65.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-trifluoromethylpyridin-3-yl.

同樣較佳為式I.66化合物，特別佳為化合物I.66.1－I.66.3434，特定言之化合物(Z,S )－I.66.1－I.66.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－三氟甲基吡啶－3－基。Also preferred are the compounds of the formula I.66, particularly preferably the compounds I.66.1-I.66.3434, in particular the compounds ( Z,S )-I.66.1-I.66.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-trifluoromethylpyridin-3-yl.

同樣較佳為式I.67化合物，特別佳為化合物I.67.1－I.67.3434，特定言之化合物(Z,S )－I.67.1－I.67.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－三氟甲基吡啶－3－基。Also preferred are the compounds of the formula I.67, particularly preferably the compounds I.67.1-I.67.3434, in particular the compounds ( Z,S )-I.67.1-I.67.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-trifluoromethylpyridin-3-yl.

同樣較佳為式I.68化合物，特別佳為化合物I.68.1－I.68.3434，特定言之化合物(Z,S )－I.68.1－I.68.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為6－三氟甲基吡啶－3－基。Also preferred are the compounds of the formula I.68, particularly preferably the compounds I.68.1-I.68.3434, in particular the compounds ( Z,S )-I.68.1-I.68.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 6-trifluoromethylpyridin-3-yl.

同樣較佳為式I.69化合物，特別佳為化合物I.69.1－I.69.3434，特定言之化合物(Z,S )－I.69.1－I.69.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－甲氧基吡啶－3－基。Also preferred are the compounds of the formula I.69, particularly preferably the compounds I.69.1-I.69.3434, in particular the compounds ( Z,S )-I.69.1-I.69.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-methoxypyridin-3-yl.

同樣較佳為式I.70化合物，特別佳為化合物I.70.1－I.70.3434，特定言之化合物(Z,S )－I.70.1－I.70.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－甲氧基吡啶－3－基。Also preferred are the compounds of the formula I.70, particularly preferably the compounds I.70.1 to I.70.3434, in particular the compounds ( Z,S )-I.70.1-I.70.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-methoxypyrid-3-yl.

同樣較佳為式I.71化合物，特別佳為化合物I.71.1－I.71.3434，特定言之化合物(Z,S )－I.71.1－I.71.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－甲氧基吡啶－3－基。Also preferred are the compounds of the formula I.71, particularly preferably the compounds I.71.1-I.71.3434, in particular the compounds ( Z,S )-I.71.1-I.71.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-methoxypyridin-3-yl.

同樣較佳為式I.72化合物，特別佳為化合物I.72.1－I.72.3434，特定言之化合物(Z,S )－I.72.1－I.72.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為6－甲氧基吡啶－3－基。Also preferred are the compounds of the formula I.72, particularly preferably the compounds I.72.1-I.72.3434, in particular the compounds ( Z,S )-I.72.1-I.72.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 6-methoxypyridin-3-yl.

同樣較佳為式I.73化合物，特別佳為化合物I.73.1－I.73.3434，特定言之化合物(Z,S )－I.73.1－I.73.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氟吡啶－3－基。Also preferred are the compounds of the formula I.73, particularly preferably the compounds I.73.1 to I.73.3434, in particular the compounds ( Z,S )-I.73.1-I.73.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-fluoropyridin-3-yl.

同樣較佳為式I.74化合物，特別佳為化合物I.74.1－I.74.3434，特定言之化合物(Z,S )－I.74.1－I.74.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－氟吡啶－3－基。Also preferred are the compounds of the formula I.74, particularly preferably the compounds I.74.1-I.74.3434, in particular the compounds ( Z,S )-I.74.1-I.74.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z, S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-fluoropyridin-3-yl.

同樣較佳為式I.75化合物，特別佳為化合物I.75.1－I.75.3434，特定言之化合物(Z,S )－I.75.1－I.75.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－氟吡啶－3－基。Also preferred are the compounds of the formula I.75, particularly preferably the compounds I.75.1-I.75.3434, in particular the compounds ( Z,S )-I.75.1-I.75.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-fluoropyridin-3-yl.

同樣較佳為式I.76化合物，特別佳為化合物I.76.1－I.76.3434，特定言之化合物(Z,S )－I.76.1－I.76.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為6－氟吡啶－3－基。Also preferred are the compounds of the formula I.76, particularly preferably the compounds I.76.1-I.76.3434, in particular the compounds ( Z,S )-I.76.1-I.76.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 6-fluoropyridin-3-yl.

同樣較佳為式I.77化合物，特別佳為化合物I.77.1－I.77.3434，特定言之化合物(Z,S )－I.77.1－I.77.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為吡啶－4－基。Also preferred are the compounds of the formula I.77, particularly preferably the compounds I.77.1-I.77.3434, in particular the compounds ( Z,S )-I.77.1-I.77.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is pyridin-4-yl.

同樣較佳為式I.78化合物，特別佳為化合物I.78.1－I.78.3434，特定言之化合物(Z,S )－I.78.1－I.78.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氟吡啶－4－基。Also preferred are the compounds of the formula I.78, particularly preferably the compounds I.78.1-I.78.3434, in particular the compounds ( Z,S )-I.78.1-I.78.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-fluoropyridin-4-yl.

同樣較佳為式I.79化合物，特別佳為化合物I.79.1－I.79.3434，特定言之化合物(Z,S )－I.79.1－I.79.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－氟吡啶－4－基。Also preferred are the compounds of the formula I.79, particularly preferably the compounds I.79.1-I.79.3434, in particular the compounds ( Z,S )-I.79.1-I.79.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-fluoropyridin-4-yl.

同樣較佳為式I.80化合物，特別佳為化合物I.80.1－I.80.3434，特定言之化合物(Z,S )－I.80.1－I.80.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－甲氧基吡啶－4－基。Also preferred are the compounds of the formula I.80, particularly preferably the compounds I.80.1-I.80.3434, in particular the compounds ( Z,S )-I.80.1-I.80.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-methoxypyridin-4-yl.

同樣較佳為式I.81化合物，特別佳為化合物I.81.1－I.81.3434，特定言之化合物(Z,S )－I.81.1－I.81.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－甲氧基吡啶－4－基。Also preferred are the compounds of the formula I.81, particularly preferably the compounds I.81.1-I.81.3434, in particular the compounds ( Z,S )-I.81.1-I.81.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-methoxypyridin-4-yl.

同樣較佳為式I.82化合物，特別佳為化合物I.82.1－I.82.3434，特定言之化合物(Z,S )－I.82.1－I.82.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－三氟甲基吡啶－4－基。Also preferred are the compounds of the formula I.82, particularly preferably the compounds I.82.1-I.82.3434, in particular the compounds ( Z,S )-I.82.1-I.82.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-trifluoromethylpyridin-4-yl.

同樣較佳為式I.83化合物，特別佳為化合物I.83.1－I.83.3434，特定言之化合物(Z,S )－I.83.1－I.83.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－三氟甲基吡啶－4－基。Also preferred are the compounds of the formula I.83, particularly preferably the compounds I.83.1 to I.83.3434, in particular the compounds ( Z,S )-I.83.1-I.83.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-trifluoromethylpyridin-4-yl.

同樣較佳為式I.84化合物，特別佳為化合物I.84.1－I.84.3434，特定言之化合物(Z,S )－I.84.1－I.84.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氯吡啶－4－基。Also preferred are the compounds of the formula I.84, particularly preferably the compounds I.84.1-I.84.3434, in particular the compounds ( Z,S )-I.84.1-I.84.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-chloropyridin-4-yl.

同樣較佳為式I.85化合物，特別佳為化合物I.85.1－I.85.3434，特定言之化合物(Z,S )－I.85.1－I.85.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－氯吡啶－4－基。Also preferred are the compounds of the formula I.85, particularly preferably the compounds I.85.1-I.85.3434, in particular the compounds ( Z,S )-I.85.1-I.85.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-chloropyridin-4-yl.

同樣較佳為式I.86化合物，特別佳為化合物I.86.1－I.86.3434，特定言之化合物(Z,S )－I.86.1－I.86.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為噻吩－2－基。Also preferred are the compounds of the formula I.86, particularly preferably the compounds I.86.1-I.86.3434, in particular the compounds ( Z,S )-I.86.1-I.86.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z, S)-I.1.1-I.1.3434 where A 2 R d R e R f is thiophen-2-yl.

同樣較佳為式I.87化合物，特別佳為化合物I.87.1－I.87.3434，特定言之化合物(Z,S )－I.87.1－I.87.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－氯噻吩－2－基。Also preferred are the compounds of the formula I.87, particularly preferably the compounds I.87.1-I.87.3434, in particular the compounds ( Z,S )-I.87.1-I.87.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-chlorothien-2-yl.

同樣較佳為式I.88化合物，特別佳為化合物I.88.1－I.88.3434，特定言之化合物(Z,S )－I.88.1－I.88.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－氯噻吩－2－基。Also preferred are the compounds of the formula I.88, particularly preferably the compounds I.88.1-I.88.3434, in particular the compounds ( Z,S )-I.88.1-I.88.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-chlorothien-2-yl.

同樣較佳為式I.89化合物，特別佳為化合物I.89.1－I.89.3434，特定言之化合物(Z,S )－I.89.1－I.89.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－氯噻吩－2－基。Also preferred are the compounds of the formula I.89, particularly preferably the compounds I.89.1-I.89.3434, in particular the compounds ( Z,S )-I.89.1-I.89.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-chlorothien-2-yl.

同樣較佳為式I.90化合物，特別佳為化合物I.90.1－I.90.3434，特定言之化合物(Z,S )－I.90.1－I.90.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－三氟甲基噻吩－2－基。Also preferred are the compounds of the formula I.90, particularly preferably the compounds I.90.1-I.90.3434, in particular the compounds ( Z,S )-I.90.1-I.90.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-trifluoromethylthiophen-2-yl.

同樣較佳為式I.91化合物，特別佳為化合物I.91.1－I.91.3434，特定言之化合物(Z,S )－I.91.1－I.91.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－三氟甲基噻吩－2－基。Also preferred are the compounds of the formula I.91, particularly preferably the compounds I.91.1-I.91.3434, in particular the compounds ( Z,S )-I.91.1-I.91.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-trifluoromethylthien-2-yl.

同樣較佳為式I.92化合物，特別佳為化合物I.92.1－I.92.3434，特定言之化合物(Z,S )－I.92.1－I.92.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－三氟甲基噻吩－2－基。Also preferred are the compounds of the formula I.92, particularly preferably the compounds I.92.1-I.92.3434, in particular the compounds ( Z,S )-I.92.1-I.92.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-trifluoromethylthien-2-yl.

同樣較佳為式I.93化合物，特別佳為化合物I.93.1－I.93.3434，特定言之化合物(Z,S )－I.93.1－I.93.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－甲氧基噻吩－2－基。Also preferred are the compounds of the formula I.93, particularly preferably the compounds I.93.1 to I.93.3434, in particular the compounds ( Z,S )-I.93.1-I.93.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-methoxythiophen-2-yl.

同樣較佳為式I.94化合物，特別佳為化合物I.94.1－I.94.3434，特定言之化合物(Z,S )－I.94.1－I.94.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－甲氧基噻吩－2－基。Also preferred are the compounds of the formula I.94, particularly preferably the compounds I.94.1-I.94.3434, in particular the compounds ( Z,S )-I.94.1-I.94.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-methoxythiophen-2-yl.

同樣較佳為式I.95化合物，特別佳為化合物I.95.1－I.95.3434，特定言之化合物(Z,S )－I.95.1－I.95.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－甲氧基噻吩－2－基。Also preferred are the compounds of the formula I.95, particularly preferably the compounds I.95.1-I.95.3434, in particular the compounds ( Z,S )-I.95.1-I.95.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-methoxythiophen-2-yl.

同樣較佳為式I.96化合物，特別佳為化合物I.96.1－I.96.3434，特定言之化合物(Z,S )－I.96.1－I.96.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－氟噻吩－2－基。Also preferred are the compounds of the formula I.96, particularly preferably the compounds I.96.1-I.96.3434, in particular the compounds ( Z,S )-I.96.1-I.96.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-fluorothien-2-yl.

同樣較佳為式I.97化合物，特別佳為化合物I.97.1－I.97.3434，特定言之化合物(Z,S )－I.97.1－I.97.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－氟噻吩－2－基。Also preferred are the compounds of the formula I.97, particularly preferably the compounds I.97.1-I.97.3434, in particular the compounds ( Z,S )-I.97.1-I.97.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-fluorothiophen-2-yl.

同樣較佳為式I.98化合物，特別佳為化合物I.98.1－I.98.3434，特定言之化合物(Z,S )－I.98.1－I.98.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－氟噻吩－2－基。Also preferred are the compounds of the formula I.98, particularly preferably the compounds I.98.1-I.98.3434, in particular the compounds ( Z,S )-I.98.1-I.98.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z, S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-fluorothiophen-2-yl.

同樣較佳為式I.99化合物，特別佳為化合物I.99.1－I.99.3434，特定言之化合物(Z,S )－I.99.1－I.99.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為噻吩－3－基。Also preferred are the compounds of the formula I.99, particularly preferably the compounds I.99.1-I.99.3434, in particular the compounds ( Z,S )-I.99.1-I.99.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is thiophen-3-yl.

同樣較佳為式I.100化合物，特別佳為化合物I.100.1－I.100.3434，特定言之化合物(Z,S )－I.100.1－I.100.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氯噻吩－3－基。Also preferred are the compounds of the formula I.100, particularly preferably the compounds I.100.1-I.100.3434, in particular the compounds ( Z,S )-I.100.1-I.100.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-chlorothien-3-yl.

同樣較佳為式I.101化合物，特別佳為化合物I.101.1－I.101.3434，特定言之化合物(Z,S )－I.101.1－I.101.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－氯噻吩－3－基。Also preferred are the compounds of the formula I.101, particularly preferably the compounds I.101.1-I.101.3434, in particular the compounds ( Z,S )-I.101.1-I.101.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-chlorothien-3-yl.

同樣較佳為式I.102化合物，特別佳為化合物I.102.1－I.102.3434，特定言之化合物(Z,S )－I.102.1－I.102.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－氯噻吩－3－基。Also preferred are the compounds of the formula I.102, particularly preferably the compounds I.102.1-I.102.3434, in particular the compounds ( Z,S )-I.102.1-I.102.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-chlorothien-3-yl.

同樣較佳為式I.103化合物，特別佳為化合物I.103.1－I.103.3434，特定言之化合物(Z,S )－I.103.1－I.103.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氟噻吩－3－基。Also preferred are the compounds of the formula I.103, particularly preferably the compounds I.103.1-I.103.3434, in particular the compounds ( Z,S )-I.103.1-I.103.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-fluorothiophen-3-yl.

同樣較佳為式I.104化合物，特別佳為化合物I.104.1－I.104.3434，特定言之化合物(Z,S )－I.104.1－I.104.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－氟噻吩－3－基。Also preferred are the compounds of the formula I.104, particularly preferably the compounds I.104.1 to I.104.3434, in particular the compounds ( Z,S )-I.104.1-I.104.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-fluorothiophen-3-yl.

同樣較佳為式I.105化合物，特別佳為化合物I.105.1－I.105.3434，特定言之化合物(Z,S )－I.105.1－I.105.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－氟噻吩－3－基。Also preferred are the compounds of the formula I.105, particularly preferably the compounds I.105.1-I.105.3434, in particular the compounds ( Z,S )-I.105.1-I.105.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-fluorothiophen-3-yl.

同樣較佳為式I.106化合物，特別佳為化合物I.106.1－I.106.3434，特定言之化合物(Z,S )－I.106.1－I.106.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－甲氧基噻吩－3－基。Also preferred are the compounds of the formula I.106, particularly preferably the compounds I.106.1-I.106.3434, in particular the compounds ( Z,S )-I.106.1-I.106.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-methoxythiophen-3-yl.

同樣較佳為式I.107化合物，特別佳為化合物I.107.1－I.107.3434，特定言之化合物(Z,S )－I.107.1－I.107.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－甲氧基噻吩－3－基。Also preferred are the compounds of the formula I.107, particularly preferably the compounds I.107.1-I.107.3434, in particular the compounds ( Z,S )-I.107.1-I.107.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-methoxythiophen-3-yl.

同樣較佳為式I.108化合物，特別佳為化合物I.108.1－I.108.3434，特定言之化合物(Z,S )－I.108.1－I.108.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－甲氧基噻吩－3－基。Also preferred are the compounds of the formula I.108, particularly preferably the compounds I.108.1-I.108.3434, in particular the compounds ( Z,S )-I.108.1-I.108.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-methoxythiophen-3-yl.

同樣較佳為式I.109化合物，特別佳為化合物I.109.1－I.109.3434，特定言之化合物(Z,S )－I.109.1－I.109.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－三氟甲基噻吩－3－基。Also preferred are the compounds of the formula I.109, particularly preferably the compounds I.109.1-I.109.3434, in particular the compounds ( Z,S )-I.109.1-I.109.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-trifluoromethylthiophen-3-yl.

同樣較佳為式I.110化合物，特別佳為化合物I.110.1－I.110.3434，特定言之化合物(Z,S )－I.110.1－I.110.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－三氟甲基噻吩－3－基。Also preferred are the compounds of the formula I.110, particularly preferably the compounds I.110.1-I.110.3434, in particular the compounds ( Z,S )-I.110.1-I.110.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-trifluoromethylthiophen-3-yl.

同樣較佳為式I.111化合物，特別佳為化合物I.111.1－I.111.3434，特定言之化合物(Z,S )－I.111.1－I.111.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－三氟甲基噻吩－3－基。Also preferred are the compounds of the formula I.111, particularly preferably the compounds I.111.1-I.111.3434, in particular the compounds ( Z,S )-I.111.1-I.111.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-trifluoromethylthiophen-3-yl.

同樣較佳為式I.112化合物，特別佳為化合物I.112.1－I.112.3434，特定言之化合物(Z,S )－I.112.1－I.112.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為呋喃－2－基。Also preferred are the compounds of the formula I.112, particularly preferably the compounds I.112.1-I.112.3434, in particular the compounds ( Z,S )-I.112.1-I.112.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is furan-2-yl.

同樣較佳為式I.113化合物，特別佳為化合物I.113.1－I.113.3434，特定言之化合物(Z,S )－I.113.1－I.113.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－氯呋喃－2－基。Also preferred are the compounds of the formula I.113, particularly preferably the compounds I.113.1-I.113.3434, in particular the compounds ( Z,S )-I.113.1-I.113.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-chlorofuran- 2 -yl.

同樣較佳為式I.114化合物，特別佳為化合物I.114.1－I.114.3434，特定言之化合物(Z,S )－I.114.1－I.114.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－氯呋喃－2－基。Also preferred are the compounds of the formula I.114, particularly preferably the compounds I.114.1-I.114.3434, in particular the compounds ( Z,S )-I.114.1-I.114.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-chlorofuran- 2 -yl.

同樣較佳為式I.115化合物，特別佳為化合物I.115.1－I.115.3434，特定言之化合物(Z,S )－I.115.1－I.115.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－氯呋喃－2－基。Also preferred are the compounds of the formula I.115, particularly preferably the compounds I.115.1-I.115.3434, in particular the compounds ( Z,S )-I.115.1-I.115.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-chlorofuran- 2 -yl.

同樣較佳為式I.116化合物，特別佳為化合物I.116.1－I.116.3434，特定言之化合物(Z,S )－I.116.1－I.116.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－氟呋喃－2－基。Also preferred are the compounds of the formula I.116, particularly preferably the compounds I.116.1-I.116.3434, in particular the compounds ( Z,S )-I.116.1-I.116.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-fluorofuran-2-yl.

同樣較佳為式I.117化合物，特別佳為化合物I.117.1－I.117.3434，特定言之化合物(Z,S )－I.117.1－I.117.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－氟呋喃－2－基。Also preferred are the compounds of the formula I.117, particularly preferably the compounds I.117.1-I.117.3434, in particular the compounds ( Z,S )-I.117.1-I.117.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z, S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-fluorofuran-2-yl.

同樣較佳為式I.118化合物，特別佳為化合物I.118.1－I.118.3434，特定言之化合物(Z,S )－I.118.1－I.118.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－氟呋喃－2－基。Also preferred are the compounds of the formula I.118, particularly preferably the compounds I.118.1-I.118.3434, in particular the compounds ( Z,S )-I.118.1-I.118.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-fluorofuran-2-yl.

同樣較佳為式I.119化合物，特別佳為化合物I.119.1－I.119.3434，特定言之化合物(Z,S )－I.119.1－I.119.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為呋喃－3－基。Also preferred are the compounds of the formula I.119, particularly preferably the compounds I.119.1-I.119.3434, in particular the compounds ( Z,S )-I.119.1-I.119.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is furan-3-yl.

同樣較佳為式I.120化合物，特別佳為化合物I.120.1－I.120.3434，特定言之化合物(Z,S )－I.120.1－I.120.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氯呋喃－3－基。Also preferred are the compounds of the formula I.120, particularly preferably the compounds I.120.1-I.120.3434, in particular the compounds ( Z,S )-I.120.1-I.120.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-chlorofuran-3-yl.

同樣較佳為式I.121化合物，特別佳為化合物I.121.1－I.121.3434，特定言之化合物(Z,S )－I.121.1－I.121.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－氯呋喃－3－基。Also preferred are the compounds of the formula I.121, particularly preferably the compounds I.121.1-I.121.3434, in particular the compounds ( Z,S )-I.121.1-I.121.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-chlorofuran-3-yl.

同樣較佳為式I.122化合物，特別佳為化合物I.122.1－I.122.3434，特定言之化合物(Z,S )－I.122.1－I.122.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－氯呋喃－3－基。Also preferred are the compounds of the formula I.122, particularly preferably the compounds I.122.1-I.122.3434, in particular the compounds ( Z,S )-I.122.1-I.122.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z, S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-chlorofuran-3-yl.

同樣較佳為式I.123化合物，特別佳為化合物I.123.1－I.123.3434，特定言之化合物(Z,S )－I.123.1－I.123.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氟呋喃－3－基。Also preferred are the compounds of the formula I.123, particularly preferably the compounds I.123.1-I.123.3434, in particular the compounds ( Z,S )-I.123.1-I.123.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-fluorofuran-3-yl.

同樣較佳為式I.124化合物，特別佳為化合物I.124.1－I.124.3434，特定言之化合物(Z,S )－I.124.1－I.124.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－氟呋喃－3－基。Also preferred are the compounds of the formula I.124, particularly preferably the compounds I.124.1-I.124.3434, in particular the compounds ( Z,S )-I.124.1-I.124.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-fluorofuran-3-yl.

同樣較佳為式I.125化合物，特別佳為化合物I.125.1－I.125.3434，特定言之化合物(Z,S )－I.125.1－I.125.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－氟呋喃－3－基。Also preferred are the compounds of the formula I.125, particularly preferably the compounds I.125.1-I.125.3434, in particular the compounds ( Z,S )-I.125.1-I.125.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z, S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-fluorofuran-3-yl.

同樣較佳為式I.126化合物，特別佳為化合物I.126.1－I.126.3434，特定言之化合物(Z,S )－I.126.1－I.126.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－氟呋喃－3－基。Also preferred are the compounds of the formula I.126, particularly preferably the compounds I.126.1-I.126.3434, in particular the compounds ( Z,S )-I.126.1-I.126.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z, S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-fluorofuran-3-yl.

同樣較佳為式I.127化合物，特別佳為化合物I.127.1－I.127.3434，特定言之化合物(Z,S )－I.127.1－I.127.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於R1 為CH3 。Also preferred are the compounds of the formula I.127, particularly preferably the compounds I.127.1-I.127.3434, in particular the compounds ( Z,S )-I.127.1-I.127.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where R 1 is CH 3 .

同樣較佳為式I.128化合物，特別佳為化合物I.128.1－I.128.3434，特定言之化合物(Z,S )－I.128.1－I.128.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氯苯基與R1 為CH3 。Also preferred are the compounds of the formula I.128, particularly preferably the compounds I.128.1-I.128.3434, in particular the compounds ( Z,S )-I.128.1-I.128.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-chlorophenyl and R 1 is CH 3 .

同樣較佳為式I.129化合物，特別佳為化合物I.129.1－I.129.3434，特定言之化合物(Z,S )－I.129.1－I.129.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－氯苯基與R1 為CH3 。Also preferred are the compounds of the formula I.129, particularly preferably the compounds I.129.1-I.129.3434, in particular the compounds ( Z,S )-I.129.1-I.129.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-chlorophenyl and R 1 is CH 3 .

同樣較佳為式I.130化合物，特別佳為化合物I.130.1－I.130.3434，特定言之化合物(Z,S )－I.130.1－I.130.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－氯苯基與R1 為CH3 。Also preferred are the compounds of the formula I.130, particularly preferably the compounds I.130.1-I.130.3434, in particular the compounds ( Z,S )-I.130.1-I.130.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-chlorophenyl and R 1 is CH 3 .

同樣較佳為式I.131化合物，特別佳為化合物I.131.1－I.131.3434，特定言之化合物(Z,S )－I.131.1－I.131.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－三氟甲基苯基與R1 為CH3 。Also preferred are the compounds of the formula I.131, particularly preferably the compounds I.131.1-I.131.3434, in particular the compounds ( Z,S )-I.131.1-I.131.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-trifluoromethylphenyl and R 1 is CH 3 .

同樣較佳為式I.132化合物，特別佳為化合物I.132.1－I.132.3434，特定言之化合物(Z,S )－I.132.1－I.132.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－三氟甲基苯基與R1 為CH3 。Also preferred are the compounds of the formula I.132, particularly preferably the compounds I.132.1-I.132.3434, in particular the compounds ( Z,S )-I.132.1-I.132.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-trifluoromethylphenyl and R 1 is CH 3 .

同樣較佳為式I.133化合物，特別佳為化合物I.133.1－I.133.3434，特定言之化合物(Z,S )－I.133.1－I.133.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－三氟甲基苯基與R1 為CH3 。Also preferred are the compounds of the formula I.133, particularly preferably the compounds I.133.1-I.133.3434, in particular the compounds ( Z,S )-I.133.1-I.133.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-trifluoromethylphenyl and R 1 is CH 3 .

同樣較佳為式I.134化合物，特別佳為化合物I.134.1－I.134.3434，特定言之化合物(Z,S )－I.134.1－I.134.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－甲氧基苯基與R1 為CH3 。Also preferred are the compounds of the formula I.134, particularly preferably the compounds I.134.1-I.134.3434, in particular the compounds ( Z,S )-I.134.1-I.134.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-methoxyphenyl and R 1 is CH 3 .

同樣較佳為式I.135化合物，特別佳為化合物I.135.1－I.135.3434，特定言之化合物(Z,S )－I.135.1－I.135.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－甲氧基苯基與R1 為CH3 。Also preferred are the compounds of the formula I.135, particularly preferably the compounds I.135.1-I.135.3434, in particular the compound ( Z,S )-I.135.1-I.135.3434, which differs from the corresponding compound I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-methoxyphenyl and R 1 is CH 3 .

同樣較佳為式I.136化合物，特別佳為化合物I.136.1－I.136.3434，特定言之化合物(Z,S )－I.136.1－I.136.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－甲氧基苯基與R1 為CH3 。Also preferred are the compounds of the formula I.136, particularly preferably the compounds I.136.1-I.136.3434, in particular the compounds ( Z,S )-I.136.1-I.136.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-methoxyphenyl and R 1 is CH 3 .

同樣較佳為式I.137化合物，特別佳為化合物I.137.1－I.137.3434，特定言之化合物(Z,S )－I.137.1－I.137.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氟苯基與R1 為CH3 。Also preferred are the compounds of the formula I.137, particularly preferably the compounds I.137.1-I.137.3434, in particular the compounds ( Z,S )-I.137.1-I.137.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-fluorophenyl and R 1 is CH 3 .

同樣較佳為式I.138化合物，特別佳為化合物I.138.1－I.138.3434，特定言之化合物(Z,S )－I.138.1－I.138.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－氟苯基與R1 為CH3 。Also preferred are the compounds of the formula I.138, particularly preferably the compounds I.138.1-I.138.3434, in particular the compounds ( Z,S )-I.138.1-I.138.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-fluorophenyl and R 1 is CH 3 .

同樣較佳為式I.139化合物，特別佳為化合物I.139.1－I.139.3434，特定言之化合物(Z,S )－I.139.1－I.139.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－氟苯基與R1 為CH3 。Also preferred are the compounds of the formula I.139, particularly preferably the compounds I.139.1-I.139.3434, in particular the compounds ( Z,S )-I.139.1-I.139.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z, S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-fluorophenyl and R 1 is CH 3 .

同樣較佳為式I.140化合物，特別佳為化合物I.140.1－I.140.3434，特定言之化合物(Z,S )－I.140.1－I.140.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－甲基苯基與R1 為CH3 。Also preferred are the compounds of the formula I.140, particularly preferably the compounds I.140.1-I.140.3434, in particular the compounds ( Z,S )-I.140.1-I.140.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-methylphenyl and R 1 is CH 3 .

同樣較佳為式I.141化合物，特別佳為化合物I.141.1－I.141.3434，特定言之化合物(Z,S )－I.141.1－I.141.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－甲基苯基與R1 為CH3 。Also preferred are the compounds of the formula I.141, particularly preferably the compounds I.141.1-I.141.3434, in particular the compounds ( Z,S )-I.141.1-I.141.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-methylphenyl and R 1 is CH 3 .

同樣較佳為式I.142化合物，特別佳為化合物I.142.1－I.142.3434，特定言之化合物(Z,S )－I.142.1－I.142.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－甲基苯基與R1 為CH3 。Also preferred are the compounds of the formula I.142, particularly preferably the compounds I.142.1-I.142.3434, in particular the compounds ( Z,S )-I.142.1-I.142.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-methylphenyl and R 1 is CH 3 .

同樣較佳為式I.143化合物，特別佳為化合物I.143.1－I.143.3434，特定言之化合物(Z,S )－I.143.1－I.143.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氯－3－甲基苯基與R1 為CH3 。Also preferred are the compounds of the formula I.143, particularly preferably the compounds I.143.1-I.143.3434, in particular the compounds ( Z,S )-I.143.1-I.143.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-chloro-3-methylphenyl and R 1 is CH 3 .

同樣較佳為式I.144化合物，特別佳為化合物I.144.1－I.144.3434，特定言之化合物(Z,S )－I.144.1－I.144.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氯－4－甲基苯基與R1 為CH3 。Also preferred are the compounds of the formula I.144, particularly preferably the compounds I.144.1-I.144.3434, in particular the compounds ( Z,S )-I.144.1-I.144.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-chloro-4-methylphenyl and R 1 is CH 3 .

同樣較佳為式I.145化合物，特別佳為化合物I.145.1－I.145.3434，特定言之化合物(Z,S )－I.145.1－I.145.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氯－5－甲基苯基與R1 為CH3 。Also preferred are the compounds of the formula I.145, particularly preferably the compounds I.145.1-I.145.3434, in particular the compounds ( Z,S )-I.145.1-I.145.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-chloro-5-methylphenyl and R 1 is CH 3 .

同樣較佳為式I.146化合物，特別佳為化合物I.146.1－I.146.3434，特定言之化合物(Z,S )－I.146.1－I.146.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氯－6－甲基苯基與R1 為CH3 。Also preferred are the compounds of the formula I.146, particularly preferably the compounds I.146.1-I.146.3434, in particular the compounds ( Z,S )-I.146.1-I.146.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-chloro-6-methylphenyl and R 1 is CH 3 .

同樣較佳為式I.147化合物，特別佳為化合物I.147.1－I.147.3434，特定言之化合物(Z,S )－I.147.1－I.147.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2,3－二氯苯基與R1 為CH3 。Also preferred are the compounds of the formula I.147, particularly preferably the compounds I.147.1-I.147.3434, in particular the compounds ( Z,S )-I.147.1-I.147.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2,3-dichlorophenyl and R 1 is CH 3 .

同樣較佳為式I.148化合物，特別佳為化合物I.148.1－I.148.3434，特定言之化合物(Z,S )－I.148.1－I.148.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2,4－二氯苯基與R1 為CH3 。Also preferred are the compounds of the formula I.148, particularly preferably the compounds I.148.1-I.148.3434, in particular the compounds ( Z,S )-I.148.1-I.148.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2,4-dichlorophenyl and R 1 is CH 3 .

同樣較佳為式I.149化合物，特別佳為化合物I.149.1－I.149.3434，特定言之化合物(Z,S )－I.149.1－I.149.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2,5－二氯苯基與R1 為CH3 。Also preferred are the compounds of the formula I.149, particularly preferably the compounds I.149.1-I.149.3434, in particular the compounds ( Z,S )-I.149.1-I.149.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2,5-dichlorophenyl and R 1 is CH 3 .

同樣較佳為式I.150化合物，特別佳為化合物I.150.1－I.150.3434，特定言之化合物(Z,S )－I.150.1－I.150.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2,6－二氯苯基與R1 為CH3 。Also preferred are the compounds of the formula I.150, particularly preferably the compounds I.150.1-I.150.3434, in particular the compounds ( Z,S )-I.150.1-I.150.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2,6-dichlorophenyl and R 1 is CH 3 .

同樣較佳為式I.151化合物，特別佳為化合物I.151.1－I.151.3434，特定言之化合物(Z,S )－I.151.1－I.151.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氯－3－氟苯基與R1 為CH3 。Also preferred are the compounds of the formula I.151, particularly preferably the compounds I.151.1-I.151.3434, in particular the compounds ( Z,S )-I.151.1-I.151.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-chloro-3-fluorophenyl and R 1 is CH 3 .

同樣較佳為式I.152化合物，特別佳為化合物I.152.1－I.152.3434，特定言之化合物(Z,S )－I.152.1－I.152.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氯－4－氟苯基與R1 為CH3 。Also preferred are the compounds of the formula I.152, particularly preferably the compounds I.152.1-I.152.3434, in particular the compounds ( Z,S )-I.152.1-I.152.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-chloro-4-fluorophenyl and R 1 is CH 3 .

同樣較佳為式I.153化合物，特別佳為化合物I.153.1－I.153.3434，特定言之化合物(Z,S )－I.153.1－I.153.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氯－5－氟苯基與R1 為CH3 。Also preferred are the compounds of the formula I.153, particularly preferably the compounds I.153.1-I.153.3434, in particular the compounds ( Z,S )-I.153.1-I.153.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-chloro-5-fluorophenyl and R 1 is CH 3 .

同樣較佳為式I.154化合物，特別佳為化合物I.154.1－I.154.3434，特定言之化合物(Z,S )－I.154.1－I.154.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氯－6－氟苯基與R1 為CH3 。Also preferred are the compounds of the formula I.154, particularly preferably the compounds I.154.1-I.154.3434, in particular the compounds ( Z,S )-I.154.1-I.154.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-chloro-6-fluorophenyl and R 1 is CH 3 .

同樣較佳為式I.155化合物，特別佳為化合物I.155.1－I.155.3434，特定言之化合物(Z,S)－I.155.1－I.155.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2,3－二氟苯基與R1 為CH3 。Also preferred are the compounds of the formula I.155, particularly preferably the compounds I.155.1-I.155.3434, in particular the compounds (Z,S)-I.155.1-I.155.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2,3-difluorophenyl and R 1 is CH 3 .

同樣較佳為式I.156化合物，特別佳為化合物I.156.1－I.156.3434，特定言之化合物(Z,S )－I.156.1－I.156.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2,4－二氟苯基與R1 為CH3 。Also preferred are the compounds of the formula I.156, particularly preferably the compounds I.156.1-I.156.3434, in particular the compounds ( Z,S )-I.156.1-I.156.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2,4-difluorophenyl and R 1 is CH 3 .

同樣較佳為式I.157化合物，特別佳為化合物I.157.1－I.157.3434，特定言之化合物(Z,S )－I.157.1－I.157.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2,5－二氟苯基與R1 為CH3 。Also preferred are the compounds of the formula I.157, particularly preferably the compounds I.157.1-I.157.3434, in particular the compounds ( Z,S )-I.157.1-I.157.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2,5-difluorophenyl and R 1 is CH 3 .

同樣較佳為式I.158化合物，特別佳為化合物I.158.1－I.158.3434，特定言之化合物(Z,S )－I.158.1－I.158.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2,6－二氟苯基與R1 為CH3 。Also preferred are the compounds of the formula I.158, particularly preferably the compounds I.158.1-I.158.3434, in particular the compounds ( Z,S )-I.158.1-I.158.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2,6-difluorophenyl and R 1 is CH 3 .

同樣較佳為式I.159化合物，特別佳為化合物I.159.1－I.159.3434，特定言之化合物(Z,S )－I.159.1－I.159.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氟－3－氯苯基與R1 為CH3 。Also preferred are the compounds of the formula I.159, particularly preferably the compounds I.159.1-I.159.3434, in particular the compounds ( Z,S )-I.159.1-I.159.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-fluoro-3-chlorophenyl and R 1 is CH 3 .

同樣較佳為式I.160化合物，特別佳為化合物I.160.1－I.160.3434，特定言之化合物(Z,S )－I.160.1－I.160.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氟－4－氯苯基與R1 為CH3 。Also preferred are the compounds of the formula I.160, particularly preferably the compounds I.160.1-I.160.3434, in particular the compounds ( Z,S )-I.160.1-I.160.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-fluoro-4-chlorophenyl and R 1 is CH 3 .

同樣較佳為式I.161化合物，特別佳為化合物I.161.1－I.161.3434，特定言之化合物(Z,S )－I.161.1－I.161.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氟－5－氯苯基與R1 為CH3 。Also preferred are the compounds of the formula I.161, particularly preferably the compounds I.161.1-I.161.3434, in particular the compounds ( Z,S )-I.161.1-I.161.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-fluoro-5-chlorophenyl and R 1 is CH 3 .

同樣較佳為式I.162化合物，特別佳為化合物I.162.1－I.162.3434，特定言之化合物(Z,S )－I.162.1－I.162.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3,4－二氟苯基與R1 為CH3 。Also preferred are the compounds of the formula I.162, particularly preferably the compounds I.162.1-I.162.3434, in particular the compounds ( Z,S )-I.162.1-I.162.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3,4-difluorophenyl and R 1 is CH 3 .

同樣較佳為式I.163化合物，特別佳為化合物I.163.1－I.163.3434，特定言之化合物(Z,S )－I.163.1－I.163.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3,5－二氟苯基與R1 為CH3 。Also preferred are the compounds of the formula I.163, particularly preferably the compounds I.163.1-I.163.3434, in particular the compounds ( Z,S )-I.163.1-I.163.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3,5-difluorophenyl and R 1 is CH 3 .

同樣較佳為式I.164化合物，特別佳為化合物I.164.1－I.164.3434，特定言之化合物(Z,S )－I.164.1－I.164.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3,4－二氯苯基與R1 為CH3 。Also preferred are the compounds of the formula I.164, particularly preferably the compounds I.164.1-I.164.3434, in particular the compounds ( Z,S )-I.164.1-I.164.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3,4-dichlorophenyl and R 1 is CH 3 .

同樣較佳為式I.165化合物，特別佳為化合物I.165.1－I.165.3434，特定言之化合物(Z,S )－I.165.1－I.165.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3,5－二氯苯基與R1 為CH3 。Also preferred are the compounds of the formula I.165, particularly preferably the compounds I.165.1-I.165.3434, in particular the compounds ( Z,S )-I.165.1-I.165.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3,5-dichlorophenyl and R 1 is CH 3 .

同樣較佳為式I.166化合物，特別佳為化合物I.166.1－I.166.3434，特定言之化合物(Z,S )－I.166.1－I.166.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－氟－4－氯苯基與R1 為CH3 。Also preferred are the compounds of the formula I.166, particularly preferably the compounds I.166.1-I.166.3434, in particular the compounds ( Z,S )-I.166.1-I.166.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-fluoro-4-chlorophenyl and R 1 is CH 3 .

同樣較佳為式I.167化合物，特別佳為化合物I.167.1－I.167.3434，特定言之化合物(Z,S )－I.167.1－I.167.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－氟－3－氯苯基與R1 為CH3 。Also preferred are the compounds of the formula I.167, particularly preferably the compounds I.167.1-I.167.3434, in particular the compounds ( Z,S )-I.167.1-I.167.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-fluoro-3-chlorophenyl and R 1 is CH 3 .

同樣較佳為式I.168化合物，特別佳為化合物I.168.1－I.168.3434，特定言之化合物(Z,S )－I.168.1－I.168.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－氟－5－氯苯基與R1 為CH3 。Also preferred are the compounds of the formula I.168, particularly preferably the compounds I.168.1-I.168.3434, in particular the compounds ( Z,S )-I.168.1-I.168.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-fluoro-5-chlorophenyl and R 1 is CH 3 .

同樣較佳為式I.169化合物，特別佳為化合物I.169.1－I.169.3434，特定言之化合物(Z,S )－I.169.1－I.169.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為吡啶－2－基與R1 為CH3 。Also preferred are the compounds of the formula I.169, particularly preferably the compounds I.169.1-I.169.3434, in particular the compounds ( Z,S )-I.169.1-I.169.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is pyridin-2-yl and R 1 is CH 3 .

同樣較佳為式I.170化合物，特別佳為化合物I.170.1－I.170.3434，特定言之化合物(Z,S )－I.170.1－I.170.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－氯吡啶－2－基與R1 為CH3 。Also preferred are the compounds of the formula I.170, particularly preferably the compounds I.170.1-I.170.3434, in particular the compounds ( Z,S )-I.170.1-I.170.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-chloropyridin-2-yl and R 1 is CH 3 .

同樣較佳為式I.171化合物，特別佳為化合物I.171.1－I.171.3434，特定言之化合物(Z,S )－I.171.1－I.171.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－氯吡啶－2－基與R1 為CH3 。Also preferred are the compounds of the formula I.171, particularly preferably the compounds I.171.1-I.171.3434, in particular the compounds ( Z,S )-I.171.1-I.171.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-chloropyridin-2-yl and R 1 is CH 3 .

同樣較佳為式I.172化合物，特別佳為化合物I.172.1－I.172.3434，特定言之化合物(Z,S )－I.172.1－I.172.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－氯吡啶－2－基與R1 為CH3 。Also preferred are the compounds of the formula I.172, particularly preferably the compounds I.172.1-I.172.3434, in particular the compounds ( Z,S )-I.172.1-I.172.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-chloropyridin-2-yl and R 1 is CH 3 .

同樣較佳為式I.173化合物，特別佳為化合物I.173.1－I.173.3434，特定言之化合物(Z,S )－I.173.1－I.173.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為6－氯吡啶－2－基與R1 為CH3 。Also preferred are the compounds of the formula I.173, particularly preferably the compounds I.173.1 to I.173.3434, in particular the compounds ( Z,S )-I.173.1-I.173.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 6-chloropyridin-2-yl and R 1 is CH 3 .

同樣較佳為式I.174化合物，特別佳為化合物I.174.1－I.174.3434，特定言之化合物(Z,S )－I.174.1－I.174.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－三氟甲基吡啶－2－基與R1 為CH3 。Also preferred are the compounds of the formula I.174, particularly preferably the compounds I.174.1-I.174.3434, in particular the compounds ( Z,S )-I.174.1-I.174.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-trifluoromethylpyridin-2-yl and R 1 is CH 3 .

同樣較佳為式I.175化合物，特別佳為化合物I.175.1－I.175.3434，特定言之化合物(Z,S )－I.175.1－I.175.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－三氟甲基吡啶－2－基與R1 為CH3 。Also preferred are the compounds of the formula I.175, particularly preferably the compounds I.175.1-I.175.3434, in particular the compounds ( Z,S )-I.175.1-I.175.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-trifluoromethylpyridin-2-yl and R 1 is CH 3 .

同樣較佳為式I.176化合物，特別佳為化合物I.176.1－I.176.3434，特定言之化合物(Z,S )－I.176.1－I.176.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－三氟甲基吡啶－2－基與R1 為CH3 。Also preferred are the compounds of the formula I.176, particularly preferably the compounds I.176.1-I.176.3434, in particular the compounds ( Z,S )-I.176.1-I.176.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-trifluoromethylpyridin-2-yl and R 1 is CH 3 .

同樣較佳為式I.177化合物，特別佳為化合物I.177.1－I.177.3434，特定言之化合物(Z,S )－I.177.1－I.177.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為6－三氟甲基吡啶－2－基與R1 為CH3 。Also preferred are the compounds of the formula I.177, particularly preferably the compounds I.177.1-I.177.3434, in particular the compounds ( Z,S )-I.177.1-I.177.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 6-trifluoromethylpyridin-2-yl and R 1 is CH 3 .

同樣較佳為式I.178化合物，特別佳為化合物I.178.1－I.178.3434，特定言之化合物(Z,S )－I.178.1－I.178.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－甲氧基吡啶－2－基與R1 為CH3 。Also preferred are the compounds of the formula I.178, particularly preferably the compounds I.178.1-I.178.3434, in particular the compounds ( Z,S )-I.178.1-I.178.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-methoxypyridin-2-yl and R 1 is CH 3 .

同樣較佳為式I.179化合物，特別佳為化合物I.179.1－I.179.3434，特定言之化合物(Z,S )－I.179.1－I.179.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－甲氧基吡啶－2－基與R1 為CH3 。Also preferred are the compounds of the formula I.179, particularly preferably the compounds I.179.1-I.179.3434, in particular the compounds ( Z,S )-I.179.1-I.179.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-methoxypyridin-2-yl and R 1 is CH 3 .

同樣較佳為式I.180化合物，特別佳為化合物I.180.1－I.180.3434，特定言之化合物(Z,S )－I.180.1－I.180.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－甲氧基吡啶－2－基與R1 為CH3 。Also preferred are the compounds of the formula I.180, particularly preferably the compounds I.180.1-I.180.3434, in particular the compounds ( Z,S )-I.180.1-I.180.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-methoxypyridin-2-yl and R 1 is CH 3 .

同樣較佳為式I.181化合物，特別佳為化合物I.181.1－I.181.3434，特定言之化合物(Z,S )－I.181.1－I.181.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為6－甲氧基吡啶－2－基與R1 為CH3 。Also preferred are the compounds of the formula I.181, particularly preferably the compounds I.181.1-I.181.3434, in particular the compounds ( Z,S )-I.181.1-I.181.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 6-methoxypyridin-2-yl and R 1 is CH 3 .

同樣較佳為式I.182化合物，特別佳為化合物I.182.1－I.182.3434，特定言之化合物(Z,S )－I.182.1－I.182.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－氟吡啶－2－基與R1 為CH3 。Also preferred are the compounds of the formula I.182, particularly preferably the compounds I.182.1-I.182.3434, in particular the compounds ( Z,S )-I.182.1-I.182.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-fluoropyridin-2-yl and R 1 is CH 3 .

同樣較佳為式I.183化合物，特別佳為化合物I.183.1－I.183.3434，特定言之化合物(Z,S )－I.183.1－I.183.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－氟吡啶－2－基與R1 為CH3 。Also preferred are the compounds of the formula I.183, particularly preferably the compounds I.183.1-I.183.3434, in particular the compounds ( Z,S )-I.183.1-I.183.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-fluoropyridin-2-yl and R 1 is CH 3 .

同樣較佳為式I.184化合物，特別佳為化合物I.184.1－I.184.3434，特定言之化合物(Z,S )－I.184.1－I.184.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－氟吡啶－2－基與R1 為CH3 。Also preferred are the compounds of the formula I.184, particularly preferably the compounds I.184.1-I.184.3434, in particular the compounds ( Z,S )-I.184.1-I.184.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-fluoropyridin-2-yl and R 1 is CH 3 .

同樣較佳為式I.185化合物，特別佳為化合物I.185.1－I.185.3434，特定言之化合物(Z,S )－I.185.1－I.185.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為6－氟吡啶－2－基與R1 為CH3 。Also preferred are the compounds of the formula I.185, particularly preferably the compounds I.185.1-I.185.3434, in particular the compounds ( Z,S )-I.185.1-I.185.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 6-fluoropyridin-2-yl and R 1 is CH 3 .

同樣較佳為式I.186化合物，特別佳為化合物I.186.1－I.186.3434，特定言之化合物(Z,S )－I.186.1－I.186.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為吡啶－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.186, particularly preferably the compounds I.186.1-I.186.3434, in particular the compounds ( Z,S )-I.186.1-I.186.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 is where A 2 R d R e R f is pyridin-3-yl and R 1 is CH 3 .

同樣較佳為式I.187化合物，特別佳為化合物I.187.1－I.187.3434，特定言之化合物(Z,S )－I.187.1－I.187.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氯吡啶－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.187, particularly preferably the compounds I.187.1-I.187.3434, in particular the compounds ( Z,S )-I.187.1-I.187.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-chloropyridin-3-yl and R 1 is CH 3 .

同樣較佳為式I.188化合物，特別佳為化合物I.188.1－I.188.3434，特定言之化合物(Z,S )－I.188.1－I.188.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－氯吡啶－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.188, particularly preferably the compounds I.188.1-I.188.3434, in particular the compounds ( Z,S )-I.188.1-I.188.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-chloropyridin-3-yl and R 1 is CH 3 .

同樣較佳為式I.189化合物，特別佳為化合物I.189.1－I.189.3434，特定言之化合物(Z,S )－I.189.1－I.189.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－氯吡啶－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.189, particularly preferably the compounds I.189.1-I.189.3434, in particular the compounds ( Z,S )-I.189.1-I.189.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-chloropyridin-3-yl and R 1 is CH 3 .

同樣較佳為式I.190化合物，特別佳為化合物I.190.1－I.190.3434，特定言之化合物(Z,S )－I.190.1－I.190.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為6－氯吡啶－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.190, particularly preferably the compounds I.190.1-I.190.3434, in particular the compounds ( Z,S )-I.190.1-I.190.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 6-chloropyridin-3-yl and R 1 is CH 3 .

同樣較佳為式I.191化合物，特別佳為化合物I.191.1－I.191.3434，特定言之化合物(Z,S )－I.191.1－I.191.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－三氟甲基吡啶－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.191, particularly preferably the compounds I.191.1-I.191.3434, in particular the compounds ( Z,S )-I.191.1-I.191.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-trifluoromethylpyridin-3-yl and R 1 is CH 3 .

同樣較佳為式I.192化合物，特別佳為化合物I.192.1－I.192.3434，特定言之化合物(Z,S )－I.192.1－I.192.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－三氟甲基吡啶－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.192, particularly preferably the compounds I.192.1-I.192.3434, in particular the compounds ( Z,S )-I.192.1-I.192.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-trifluoromethylpyridin-3-yl and R 1 is CH 3 .

同樣較佳為式I.193化合物，特別佳為化合物I.193.1－I.193.3434，特定言之化合物(Z,S )－I.193.1－I.193.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－三氟甲基吡啶－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.193, particularly preferably the compounds I.193.1 to I.193.3434, in particular the compounds ( Z,S )-I.193.1-I.193.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-trifluoromethylpyridin-3-yl and R 1 is CH 3 .

同樣較佳為式I.194化合物，特別佳為化合物I.194.1－I.194.3434，特定言之化合物(Z,S )－I.194.1－I.194.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為6－三氟甲基吡啶－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.194, particularly preferably the compounds I.194.1-I.194.3434, in particular the compounds ( Z,S )-I.194.1-I.194.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 6-trifluoromethylpyridin-3-yl and R 1 is CH 3 .

同樣較佳為式I.195化合物，特別佳為化合物I.195.1－I.195.3434，特定言之化合物(Z,S )－I.195.1－I.195.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－甲氧基吡啶－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.195, particularly preferably the compounds I.195.1-I.195.3434, in particular the compounds ( Z,S )-I.195.1-I.195.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-methoxypyridin-3-yl and R 1 is CH 3 .

同樣較佳為式I.196化合物，特別佳為化合物I.196.1－I.196.3434，特定言之化合物(Z,S )－I.196.1－I.196.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－甲氧基吡啶－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.196, particularly preferably the compounds I.196.1-I.196.3434, in particular the compounds ( Z,S )-I.196.1-I.196.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-methoxypyridin-3-yl and R 1 is CH 3 .

同樣較佳為式I.197化合物，特別佳為化合物I.197.1－I.197.3434，特定言之化合物(Z,S )－I.197.1－I.197.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－甲氧基吡啶－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.197, particularly preferably the compounds I.197.1-I.197.3434, in particular the compounds ( Z,S )-I.197.1-I.197.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-methoxypyridin-3-yl and R 1 is CH 3 .

同樣較佳為式I.198化合物，特別佳為化合物I.198.1－I.198.3434，特定言之化合物(Z,S )－I.198.1－I.198.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為6－甲氧基吡啶－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.198, particularly preferably the compounds I.198.1-I.198.3434, in particular the compounds ( Z,S )-I.198.1-I.198.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 6-methoxypyridin-3-yl and R 1 is CH 3 .

同樣較佳為式I.199化合物，特別佳為化合物I.199.1－I.199.3434，特定言之化合物(Z,S )－I.199.1－I.199.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氟吡啶－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.199, particularly preferably the compounds I.199.1-I.199.3434, in particular the compounds ( Z,S )-I.199.1-I.199.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-fluoropyridin-3-yl and R 1 is CH 3 .

同樣較佳為式I.200化合物，特別佳為化合物I.200.1－I.200.3434，特定言之化合物(Z,S )－I.200.1－I.200.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－氟吡啶－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.200, particularly preferably the compound I.200.1-I.200.3434, in particular the compound ( Z,S )-I.200.1-I.200.3434, which differs from the corresponding compound I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-fluoropyridin-3-yl and R 1 is CH 3 .

同樣較佳為式I.201化合物，特別佳為化合物I.201.1－I.201.3434，特定言之化合物(Z,S )－I.201.1－I.201.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－氟吡啶－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.201, particularly preferably the compounds I.201.1-I.201.3434, in particular the compounds ( Z,S )-I.201.1-I.201.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-fluoropyridin-3-yl and R 1 is CH 3 .

同樣較佳為式I.202化合物，特別佳為化合物I.202.1－I.202.3434，特定言之化合物(Z,S )－I.202.1－I.202.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為6－氟吡啶－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.202, particularly preferably the compounds I.202.1-I.202.3434, in particular the compounds ( Z,S )-I.202.1-I.202.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 6-fluoropyridin-3-yl and R 1 is CH 3 .

同樣較佳為式I.203化合物，特別佳為化合物I.203.1－I.203.3434，特定言之化合物(Z,S )－I.203.1－I.203.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為吡啶－4－基與R1 為CH3 。Also preferred are the compounds of the formula I.203, particularly preferably the compounds I.203.1-I.203.3434, in particular the compounds ( Z,S )-I.203.1-I.203.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is pyridin-4-yl and R 1 is CH 3 .

同樣較佳為式I.204化合物，特別佳為化合物I.204.1－I.204.3434，特定言之化合物(Z,S )－I.204.1－I.204.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氟吡啶－4－基與R1 為CH3 。Also preferred are the compounds of the formula I.204, particularly preferably the compounds I.204.1-I.204.3434, in particular the compounds ( Z,S )-I.204.1-I.204.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-fluoropyridin-4-yl and R 1 is CH 3 .

同樣較佳為式I.205化合物，特別佳為化合物I.205.1－I.205.3434，特定言之化合物(Z,S )－I.205.1－I.205.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－氟吡啶－4－基與R1 為CH3 。Also preferred are the compounds of the formula I.205, particularly preferably the compounds I.205.1-I.205.3434, in particular the compounds ( Z,S )-I.205.1-I.205.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-fluoropyridin-4-yl and R 1 is CH 3 .

同樣較佳為式I.206化合物，特別佳為化合物I.206.1－I.206.3434，特定言之化合物(Z,S )－I.206.1－I.206.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－甲氧基吡啶－4－基與R1 為CH3 。Also preferred are the compounds of the formula I.206, particularly preferably the compounds I.206.1-I.206.3434, in particular the compounds ( Z,S )-I.206.1-I.206.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-methoxypyridin-4-yl and R 1 is CH 3 .

同樣較佳為式I.207化合物，特別佳為化合物I.207.1－I.207.3434，特定言之化合物(Z,S )－I.207.1－I.207.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－甲氧基吡啶－4－基與R1 為CH3 。Also preferred are the compounds of the formula I.207, particularly preferably the compounds I.207.1-I.207.3434, in particular the compounds ( Z,S )-I.207.1-I.207.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-methoxypyridin-4-yl and R 1 is CH 3 .

同樣較佳為式I.208化合物，特別佳為化合物I.208.1－I.208.3434，特定言之化合物(Z,S )－I.208.1－I.208.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－三氟甲基吡啶－4－基與R1 為CH3 。Also preferred are the compounds of the formula I.208, particularly preferably the compounds I.208.1-I.208.3434, in particular the compounds ( Z,S )-I.208.1-I.208.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-trifluoromethylpyridin-4-yl and R 1 is CH 3 .

同樣較佳為式I.209化合物，特別佳為化合物I.209.1－I.209.3434，特定言之化合物(Z,S )－I.209.1－I.209.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－三氟甲基吡啶－4－基與R1 為CH3 。Also preferred are the compounds of the formula I.209, particularly preferably the compounds I.209.1-I.209.3434, in particular the compounds ( Z,S )-I.209.1-I.209.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-trifluoromethylpyridin-4-yl and R 1 is CH 3 .

同樣較佳為式I.210化合物，特別佳為化合物I.210.1－I.210.3434，特定言之化合物(Z,S )－I.210.1－I.210.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氯吡啶－4－基與R1 為CH3 。Also preferred are the compounds of the formula I.210, particularly preferably the compound I.210.1-I.210.3434, in particular the compound ( Z,S )-I.210.1-I.210.3434, which differs from the corresponding compound I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-chloropyridin-4-yl and R 1 is CH 3 .

同樣較佳為式I.211化合物，特別佳為化合物I.211.1－I.211.3434，特定言之化合物(Z,S )－I.211.1－I.211.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－氯吡啶－4－基與R1 為CH3 。Also preferred are the compounds of the formula I.211, particularly preferably the compounds I.211.1-I.211.3434, in particular the compounds ( Z,S )-I.211.1-I.211.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-chloropyridin-4-yl and R 1 is CH 3 .

同樣較佳為式I.212化合物，特別佳為化合物I.212.1－I.212.3434，特定言之化合物(Z,S )－I.212.1－I.212.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為噻吩－2－基與R1 為CH3 。Also preferred are the compounds of the formula I.212, particularly preferably the compounds I.212.1-I.212.3434, in particular the compounds ( Z,S )-I.212.1-I.212.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is thiophen-2-yl and R 1 is CH 3 .

同樣較佳為式I.213化合物，特別佳為化合物I.213.1－I.213.3434，特定言之化合物(Z,S )－I.213.1－I.213.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－氯噻吩－2－基與R1 為CH3 。Also preferred are the compounds of the formula I.213, particularly preferably the compounds I.213.1-I.213.3434, in particular the compounds ( Z,S )-I.213.1-I.213.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-chlorothien-2-yl and R 1 is CH 3 .

同樣較佳為式I.214化合物，特別佳為化合物I.214.1－I.214.3434，特定言之化合物(Z,S )－I.214.1－I.214.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－氯噻吩－2－基與R1 為CH3 。Also preferred are the compounds of the formula I.214, particularly preferably the compounds I.214.1-I.214.3434, in particular the compounds ( Z,S )-I.214.1-I.214.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-chlorothien-2-yl and R 1 is CH 3 .

同樣較佳為式I.215化合物，特別佳為化合物I.215.1－I.215.3434，特定言之化合物(Z,S )－I.215.1－I.215.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－氯噻吩－2－基與R1 為CH3 。Also preferred are the compounds of the formula I.215, particularly preferably the compounds I.215.1-I.215.3434, in particular the compounds ( Z,S )-I.215.1-I.215.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-chlorothien-2-yl and R 1 is CH 3 .

同樣較佳為式I.216化合物，特別佳為化合物I.216.1－I.216.3434，特定言之化合物(Z,S )－I.216.1－I.216.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－三氟甲基噻吩－2－基與R1 為CH3 。Also preferred are the compounds of the formula I.216, particularly preferably the compounds I.216.1-I.216.3434, in particular the compound ( Z,S )-I.216.1-I.216.3434, which differs from the corresponding compound I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-trifluoromethylthiophen-2-yl and R 1 is CH 3 .

同樣較佳為式I.217化合物，特別佳為化合物I.217.1－I.217.3434，特定言之化合物(Z,S )－I.217.1－I.217.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－三氟甲基噻吩－2－基與R1 為CH3 。Also preferred are the compounds of the formula I.217, particularly preferably the compounds I.217.1-I.217.3434, in particular the compounds ( Z,S )-I.217.1-I.217.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-trifluoromethylthiophen-2-yl and R 1 is CH 3 .

同樣較佳為式I.218化合物，特別佳為化合物I.218.1－I.218.3434，特定言之化合物(Z,S )－I.218.1－I.218.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－三氟甲基噻吩－2－基與R1 為CH3 。Also preferred are the compounds of the formula I.218, particularly preferably the compounds I.218.1-I.218.3434, in particular the compounds ( Z,S )-I.218.1-I.218.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-trifluoromethylthien-2-yl and R 1 is CH 3 .

同樣較佳為式I.219化合物，特別佳為化合物I.219.1－I.219.3434，特定言之化合物(Z,S )－I.219.1－I.219.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－甲氧基噻吩－2－基與R1 為CH3 。Also preferred are the compounds of the formula I.219, particularly preferably the compounds I.219.1-I.219.3434, in particular the compounds ( Z,S )-I.219.1-I.219.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-methoxythiophen-2-yl and R 1 is CH 3 .

同樣較佳為式I.220化合物，特別佳為化合物I.220.1－I.220.3434，特定言之化合物(Z,S )－I.220.1－I.220.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－甲氧基噻吩－2－基與R1 為CH3 。Also preferred are compounds of the formula I.220, particularly preferably the compound I.220.1-I.220.3434, in particular the compound ( Z,S )-I.220.1-I.220.3434, which differs from the corresponding compound I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-methoxythiophen-2-yl and R 1 is CH 3 .

同樣較佳為式I.221化合物，特別佳為化合物I.221.1－I.221.3434，特定言之化合物(Z,S )－I.221.1－I.221.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－甲氧基噻吩－2－基與R1 為CH3 。Also preferred are the compounds of the formula I.221, particularly preferably the compounds I.221.1-I.221.3434, in particular the compounds ( Z,S )-I.221.1-I.221.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-methoxythiophen-2-yl and R 1 is CH 3 .

同樣較佳為式I.222化合物，特別佳為化合物I.222.1－I.222.3434，特定言之化合物(Z,S )－I.222.1－I.222.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－氟噻吩－2－基與R1 為CH3 。Also preferred are the compounds of the formula I.222, particularly preferably the compounds I.222.1-I.222.3434, in particular the compounds ( Z,S )-I.222.1-I.222.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-fluorothiophen-2-yl and R 1 is CH 3 .

同樣較佳為式I.223化合物，特別佳為化合物I.223.1－I.223.3434，特定言之化合物(Z,S )－I.223.1－I.223.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－氟噻吩－2－基與R1 為CH3 。Also preferred are the compounds of the formula I.223, particularly preferably the compounds I.223.1-I.223.3434, in particular the compounds ( Z,S )-I.223.1-I.223.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-fluorothiophen-2-yl and R 1 is CH 3 .

同樣較佳為式I.224化合物，特別佳為化合物I.224.1－I.224.3434，特定言之化合物(Z,S )－I.224.1－I.224.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－氟噻吩－2－基與R1 為CH3 。Also preferred are the compounds of the formula I.224, particularly preferably the compounds I.224.1-I.224.3434, in particular the compounds ( Z,S )-I.224.1-I.224.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-fluorothiophen-2-yl and R 1 is CH 3 .

同樣較佳為式I.225化合物，特別佳為化合物I.225.1－I.225.3434，特定言之化合物(Z,S )－I.225.1－I.225.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為噻吩－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.225, particularly preferably the compounds I.225.1-I.225.3434, in particular the compounds ( Z,S )-I.225.1-I.225.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is thiophen-3-yl and R 1 is CH 3 .

同樣較佳為式I.226化合物，特別佳為化合物I.226.1－I.226.3434，特定言之化合物(Z,S )－I.226.1－I.226.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氯噻吩－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.226, particularly preferably the compounds I.226.1-I.226.3434, in particular the compounds ( Z,S )-I.226.1-I.226.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-chlorothiophen-3-yl and R 1 is CH 3 .

同樣較佳為式I.227化合物，特別佳為化合物I.227.1－I.227.3434，特定言之化合物(Z,S )－I.227.1－I.227.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－氯噻吩－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.227, particularly preferably the compounds I.227.1-I.227.3434, in particular the compounds ( Z,S )-I.227.1-I.227.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-chlorothiophen-3-yl and R 1 is CH 3 .

同樣較佳為式I.228化合物，特別佳為化合物I.228.1－I.228.3434，特定言之化合物(Z,S )－I.228.1－I.228.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－氯噻吩－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.228, particularly preferably the compounds I.228.1-I.228.3434, in particular the compounds ( Z,S )-I.228.1-I.228.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-chlorothiophen-3-yl and R 1 is CH 3 .

同樣較佳為式I.229化合物，特別佳為化合物I.229.1－I.229.3434，特定言之化合物(Z,S )－I.229.1－I.229.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氟噻吩－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.229, particularly preferably the compounds I.229.1-I.229.3434, in particular the compounds ( Z,S )-I.229.1-I.229.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-fluorothiophen-3-yl and R 1 is CH 3 .

同樣較佳為式I.230化合物，特別佳為化合物I.230.1－I.230.3434，特定言之化合物(Z,S )－I.230.1－I.230.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－氟噻吩－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.230, particularly preferably the compounds I.230.1-I.230.3434, in particular the compounds ( Z,S )-I.230.1-I.230.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-fluorothiophen-3-yl and R 1 is CH 3 .

同樣較佳為式I.231化合物，特別佳為化合物I.231.1－I.231.3434，特定言之化合物(Z,S )－I.231.1－I.231.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－氟噻吩－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.231, particularly preferably the compounds I.231.1-I.231.3434, in particular the compounds ( Z,S )-I.231.1-I.231.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-fluorothiophen-3-yl and R 1 is CH 3 .

同樣較佳為式I.232化合物，特別佳為化合物I.232.1－I.232.3434，特定言之化合物(Z,S )－I.232.1－I.232.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－甲氧基噻吩－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.232, particularly preferably the compounds I.232.1-I.232.3434, in particular the compounds ( Z,S )-I.232.1-I.232.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-methoxythiophen-3-yl and R 1 is CH 3 .

同樣較佳為式I.233化合物，特別佳為化合物I.233.1－I.233.3434，特定言之化合物(Z,S )－I.233.1－I.233.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－甲氧基噻吩－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.233, particularly preferably the compounds I.233.1-I.233.3434, in particular the compounds ( Z,S )-I.233.1-I.233.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-methoxythiophen-3-yl and R 1 is CH 3 .

同樣較佳為式I.234化合物，特別佳為化合物I.234.1－I.234.3434，特定言之化合物(Z,S )－I.234.1－I.234.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－甲氧基噻吩－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.234, particularly preferably the compounds I.234.1-I.234.3434, in particular the compounds ( Z,S )-I.234.1-I.234.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-methoxythiophen-3-yl and R 1 is CH 3 .

同樣較佳為式I.235化合物，特別佳為化合物I.235.1－I.235.3434，特定言之化合物(Z,S )－I.235.1－I.235.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－三氟甲基噻吩－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.235, particularly preferably the compounds I.235.1-I.235.3434, in particular the compounds ( Z,S )-I.235.1-I.235.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-trifluoromethylthiophen-3-yl and R 1 is CH 3 .

同樣較佳為式I.236化合物，特別佳為化合物I.236.1－I.236.3434，特定言之化合物(Z,S )－I.236.1－I.236.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－三氟甲基噻吩－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.236, particularly preferably the compounds I.236.1-I.236.3434, in particular the compounds ( Z,S )-I.236.1-I.236.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-trifluoromethylthiophen-3-yl and R 1 is CH 3 .

同樣較佳為式I.237化合物，特別佳為化合物I.237.1－I.237.3434，特定言之化合物(Z,S )－I.237.1－I.237.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－三氟甲基噻吩－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.237, particularly preferably the compounds I.237.1-I.237.3434, in particular the compounds ( Z,S )-I.237.1-I.237.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-trifluoromethylthiophen-3-yl and R 1 is CH 3 .

同樣較佳為式I.238化合物，特別佳為化合物I.238.1－I.238.3434，特定言之化合物(Z,S )－I.238.1－I.238.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為呋喃－2－基與R1 為CH3 。Also preferred are the compounds of the formula I.238, particularly preferably the compounds I.238.1-I.238.3434, in particular the compounds ( Z,S )-I.238.1-I.238.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 is where A 2 R d R e R f is furan-2-yl and R 1 is CH 3 .

同樣較佳為式I.239化合物，特別佳為化合物I.239.1－I.239.3434，特定言之化合物(Z,S )－I.239.1－I.239.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－氯呋喃－2－基與R1 為CH3 。Also preferred are the compounds of the formula I.239, particularly preferably the compounds I.239.1-I.239.3434, in particular the compounds ( Z,S )-I.239.1-I.239.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-chlorofuran- 2 -yl and R 1 is CH 3 .

同樣較佳為式I.240化合物，特別佳為化合物I.240.1－I.240.3434，特定言之化合物(Z,S )－I.240.1－I.240.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－氯呋喃－2－基與R1 為CH3 。Also preferred are compounds of the formula I.240, particularly preferably the compound I.240.1-I.240.3434, in particular the compound ( Z,S )-I.240.1-I.240.3434, which differs from the corresponding compound I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-chlorofuran- 2 -yl and R 1 is CH 3 .

同樣較佳為式I.241化合物，特別佳為化合物I.241.1－I.241.3434，特定言之化合物(Z,S )－I.241.1－I.241.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－氯呋喃－2－基與R1 為CH3 。Also preferred are the compounds of the formula I.241, particularly preferably the compounds I.241.1-I.241.3434, in particular the compounds ( Z,S )-I.241.1-I.241.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-chlorofuran- 2 -yl and R 1 is CH 3 .

同樣較佳為式I.242化合物，特別佳為化合物I.242.1－I.242.3434，特定言之化合物(Z,S )－I.242.1－I.242.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為3－氟呋喃－2－基與R1 為CH3 。Also preferred are compounds of the formula I.242, particularly preferably the compound I.242.1-I.242.3434, in particular the compound ( Z,S )-I.242.1-I.242.3434, which differs from the corresponding compound I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 3-fluorofuran-2-yl and R 1 is CH 3 .

同樣較佳為式I.243化合物，特別佳為化合物I.243.1－I.243.3434，特定言之化合物(Z,S )－I.243.1－I.243.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－氟呋喃－2－基與R1 為CH3 。Also preferred are the compounds of the formula I.243, particularly preferably the compounds I.243.1-I.243.3434, in particular the compounds ( Z,S )-I.243.1-I.243.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-fluorofuran-2-yl and R 1 is CH 3 .

同樣較佳為式I.244化合物，特別佳為化合物I.244.1－I.244.3434，特定言之化合物(Z,S )－I.244.1－I.244.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－氟呋喃－2－基與R1 為CH3 。Also preferred are the compounds of the formula I.244, particularly preferably the compounds I.244.1-I.244.3434, in particular the compounds ( Z,S )-I.244.1-I.244.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-fluorofuran-2-yl and R 1 is CH 3 .

同樣較佳為式I.245化合物，特別佳為化合物I.245.1－I.245.3434，特定言之化合物(Z,S )－I.245.1－I.245.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為呋喃－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.245, particularly preferably the compounds I.245.1-I.245.3434, in particular the compounds ( Z,S )-I.245.1-I.245.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is furan-3-yl and R 1 is CH 3 .

同樣較佳為式I.246化合物，特別佳為化合物I.246.1－I.246.3434，特定言之化合物(Z,S )－I.246.1－I.246.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氯呋喃－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.246, particularly preferably the compounds I.246.1-I.246.3434, in particular the compound ( Z,S )-I.246.1-I.246.3434, which differs from the corresponding compound I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-chlorofuran-3-yl and R 1 is CH 3 .

同樣較佳為式I.247化合物，特別佳為化合物I.247.1－I.247.3434，特定言之化合物(Z,S )－I.247.1－I.247.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－氯呋喃－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.247, particularly preferably the compounds I.247.1-I.247.3434, in particular the compounds ( Z,S )-I.247.1-I.247.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-chlorofuran-3-yl and R 1 is CH 3 .

同樣較佳為式I.248化合物，特別佳為化合物I.248.1－I.248.3434，特定言之化合物(Z,S )－I.248.1－I.248.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－氯呋喃－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.248, particularly preferably the compounds I.248.1-I.248.3434, in particular the compounds ( Z,S )-I.248.1-I.248.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-chlorofuran-3-yl and R 1 is CH 3 .

同樣較佳為式I.249化合物，特別佳為化合物I.249.1－I.249.3434，特定言之化合物(Z,S )－I.249.1－I.249.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為2－氟呋喃－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.249, particularly preferably the compounds I.249.1-I.249.3434, in particular the compounds ( Z,S )-I.249.1-I.249.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 2-fluorofuran-3-yl and R 1 is CH 3 .

同樣較佳為式I.250化合物，特別佳為化合物I.250.1－I.250.3434，特定言之化合物(Z,S )－I.250.1－I.250.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為4－氟呋喃－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.250, particularly preferably the compound I.250.1-I.250.3434, in particular the compound ( Z,S )-I.250.1-I.250.3434, which differs from the corresponding compound I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 4-fluorofuran-3-yl and R 1 is CH 3 .

同樣較佳為式I.251化合物，特別佳為化合物I.251.1－I.251.3434，特定言之化合物(Z,S )－I.251.1－I.251.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－氟呋喃－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.251, particularly preferably the compounds I.251.1-I.251.3434, in particular the compounds ( Z,S )-I.251.1-I.251.3434, which differ from the corresponding compounds I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-fluorofuran-3-yl and R 1 is CH 3 .

同樣較佳為式I.252化合物，特別佳為化合物I.252.1－I.252.3434，特定言之化合物(Z,S )－I.252.1－I.252.3434，其不同於相應化合物I.1.1－I.1.3434或(Z,S)－I.1.1－I.1.3434之處在於A2 Rd Re Rf 為5－氟呋喃－3－基與R1 為CH3 。Also preferred are the compounds of the formula I.252, particularly preferably the compound I.252.1-I.252.3434, in particular the compound ( Z,S )-I.252.1-I.252.3434, which differs from the corresponding compound I.1.1-I .1.3434 or (Z,S)-I.1.1-I.1.3434 where A 2 R d R e R f is 5-fluorofuran-3-yl and R 1 is CH 3 .

式I哌化合物可依合成有機化合物之標準方法，經由多種不同途徑製備，例如：依下文更詳細說明之方法：Formula I The compounds can be prepared by a variety of different routes according to standard methods for the synthesis of organic compounds, for example, as described in more detail below:

製法ASystem A

式I化合物可例如：類似文獻中已知方法，由相應之式II醇前體脫水製得。The compounds of formula I can be prepared, for example, by methods known in the literature, by dehydration of the corresponding alcohol precursors of formula II.

因此，本發明進一步提供一種製備根據本發明通式I哌化合物之方法，其包括由式II化合物反應 其中代號A1 、A2 、R1 、R2 、R3 、R4 、R5 、R6 、Ra 、Rb 、Rc 、Rd 、Re 與Rf 如式I化合物之定義，(A.1)產生式III化合物 其中LG為脫離基，然後自化合物III中消去化合物H－LG，產生相應化合物I；或(A.2)若LG為OH，則由式II化合物脫水，可視需要於水之存在下進行，產生相應化合物I。Accordingly, the present invention further provides a preparation of the formula I according to the present invention. a method of a compound comprising reacting a compound of formula II Wherein the codes A 1 , A 2 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R a , R b , R c , R d , R e and R f are as defined for the compound of formula I, (A.1) Production of a compound of formula III Wherein LG is a cleavage group, and then the compound H-LG is eliminated from the compound III to produce the corresponding compound I; or (A.2) if LG is OH, the compound of the formula II is dehydrated, optionally in the presence of water, to produce Corresponding compound I.

代號A1 、A2 、R1 、R2 、R3 、R4 、R5 、R6 、Ra 、Rb 、Rc 、Rd 、Re 與Rf 之較佳定義可參見上文。下文中說明根據本發明製法之較佳具體實施例。Preferred definitions of the codes A 1 , A 2 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R a , R b , R c , R d , R e and R f can be found above. . Preferred embodiments of the process according to the present invention are described below.

A.1項第一項(A.1項)中，先轉化化合物II之醇官能基形成合適脫離基，然後可呈化合物H－LG消去。消去反應最好在合適鹼之存在下進行。下列反應圖說明本反應。In item A.1 (item A.1), the alcohol functional group of compound II is first converted to form a suitable cleavage group, which can then be eliminated as compound H-LG. The elimination reaction is preferably carried out in the presence of a suitable base. The following reaction scheme illustrates the reaction.

式II中，代號A1 、A2 、R1 －R6 、Ra 、Rb 、Rc 、Rd 、Re 與Rf 如式I之定義。LG為脫離基。In Formula II, the symbols A 1 , A 2 , R 1 - R 6 , R a , R b , R c , R d , R e and R f are as defined in Formula I. LG is off the base.

脫離基LG為很容易由羥基製備之常用脫離基。其實例為4－甲苯磺醯基氧(LG＝－O－SO2 C6 H4 CH3 )、三氟甲磺醯基氧(LG＝－O－SO2 CF3 )與甲磺醯基氧(LG＝－O－SO2 CH3 )，後者特別適合。此等脫離基係依據習知方法引進，例如：由醇II與鹼反應後，與適當磺醯氯反應，例如：使用甲磺醯氯或三氟甲磺醯氯。合適鹼類為下文消去反應中所列之鹼類。然而，最好使用可溶於有機溶劑之鹼，例如：下文述及之胺類或氮雜環。特定言之，使用吡啶或經取代之吡啶，如：二甲基胺基吡啶、吡啶二羧酸或三甲基吡啶或其混合物。宜選用有機鹼，因為其亦可作為溶劑使用。The leaving group LG is a commonly used leaving group which is easily prepared from a hydroxyl group. Examples thereof are 4-toluenesulfonyloxy (LG=-O-SO 2 C 6 H 4 CH 3 ), trifluoromethanesulfonyloxy (LG=-O-SO 2 CF 3 ) and methanesulfonyloxyl (LG=-O-SO 2 CH 3 ), the latter is particularly suitable. These detachment groups are introduced according to conventional methods, for example, by reacting an alcohol II with a base and reacting with a suitable sulfonium chloride, for example, using methanesulfonium chloride or trifluoromethanesulfonium chloride. Suitable bases are the bases listed in the elimination reaction below. However, it is preferred to use a base which is soluble in an organic solvent, for example, an amine or a nitrogen heterocycle as described below. In particular, pyridine or substituted pyridine such as dimethylaminopyridine, dipicolinic acid or trimethylpyridine or a mixture thereof is used. An organic base should be used as it can also be used as a solvent.

適合消去反應之鹼類一般為無機化合物如：鹼金屬與鹼土金屬氫氧化物，如：氫氧化鋰、氫氧化鈉、氫氧化鉀或氫氧化鈣、氨水溶液、鹼金屬或鹼土金屬氧化物，如：氧化鋰、氧化鈉、氧化鈣與氧化鎂、鹼金屬與鹼土金屬氫化物，如：氫化鋰、氫化鈉、氫化鉀與氫化鈣、鹼金屬胺化物，如：胺化鋰，例如：二異丙基胺化鋰、胺化鈉與胺化鉀、鹼金屬與鹼土金屬碳酸鹽，如：碳酸鋰、碳酸鉀、碳酸銫與碳酸鈣，及鹼金屬碳酸氫鹽，如：碳酸氫鈉、有機金屬化合物，特定言之鹼金屬烷化物，如：甲基鋰、丁基鋰與苯基鋰、烷基鎂鹵化物，如：甲基鎂化氯，及鹼金屬與鹼土金屬醇鹽，如：甲醇鈉、乙醇鈉、乙醇鉀、第三丁醇鉀、第三戊醇鉀與二甲氧基鎂，及有機鹼類，例如：第三胺類，如：三甲基胺、三乙基胺、二異丙基乙基胺、2－羥基吡啶與N－甲基哌啶、吡啶、經取代之吡啶，如：三甲基吡啶、吡啶二羧酸與4－二甲基胺基吡啶，及雙環胺類。當然亦可使用不同鹼類之混合物。The bases suitable for the elimination reaction are generally inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide, aqueous ammonia solution, alkali metal or alkaline earth metal oxide, Such as: lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydride, such as: lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amination, such as: lithium amination, for example: two Lithium isopropylation, sodium amination and potassium amination, alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate, cesium carbonate and calcium carbonate, and alkali metal hydrogencarbonates such as sodium hydrogencarbonate, Organometallic compounds, in particular alkali metal alkylates, such as: methyl lithium, butyl lithium and phenyl lithium, alkyl magnesium halides, such as: methyl magnesium chloride, and alkali metal and alkaline earth metal alkoxides, such as : sodium methoxide, sodium ethoxide, potassium ethoxide, potassium butoxide, potassium pentaerythritol and magnesium dimethoxylate, and organic bases, such as: tertiary amines, such as: trimethylamine, triethyl Amine, diisopropylethylamine, 2-hydroxypyridine and N-methyl , Pyridine, substituted pyridine of, such as: collidine, pyridine dicarboxylic acid with 4-dimethylaminopyridine, and bicyclic amines. It is of course also possible to use mixtures of different bases.

然而特別合適之鹼類為具有足夠鹼性，但實質上非親核性之鹼類，例如：立體上受遮蔽之鹼金屬醇鹽，例如：鹼金屬第三丁醇鹽，如：第三丁醇鉀，特定言之環狀脒類，如：DBU(1,8－重氮雙環[5.4.0]十一碳－7－烯)與DBN(1,5－重氮環[3.4.0]壬－5－烯)。較佳為使用最後述及之脒類。However, particularly suitable bases are bases which are sufficiently basic but substantially non-nucleophilic, for example: stereoscopically masked alkali metal alkoxides, for example: alkali metal tert-butoxides, such as: third Potassium alkoxide, specifically a cyclic steroid such as DBU (1,8-diazobicyclo[5.4.0]undec-7-ene) and DBN (1,5-diazonium ring [3.4.0]壬-5-ene). Preferably, the last mentioned genus is used.

該消去反應通常在溶劑中進行，較佳為在惰性有機溶劑中。合適惰性有機溶劑包括芳香烴類，如：甲苯、鄰－、間－與對－甲苯，鹵化烴類，如：二氯甲烷、二氯乙烷、氯仿與氯苯，醚類，如：***、二異丙基醚、第三丁基甲基醚、二烷、苯甲醚與四氫呋喃，腈類，如：乙腈與丙腈，酮類，如：丙酮、甲基乙基酮、二乙基酮與第三丁基甲基酮，醇類，如：甲醇、乙醇、正丙醇、異丙醇、正丁醇、第三丁醇，水與二甲亞碸、二甲基甲醯胺與二甲基乙醯胺，及嗎啉與N－甲基嗎啉。亦可使用如上述溶劑之混合物。較佳為使用四氫呋喃。The elimination reaction is usually carried out in a solvent, preferably in an inert organic solvent. Suitable inert organic solvents include aromatic hydrocarbons such as toluene, o-, m- and p-toluene, halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform and chlorobenzene, ethers such as diethyl ether, Diisopropyl ether, tert-butyl methyl ether, two Alkanes, anisole and tetrahydrofuran, nitriles, such as: acetonitrile and propionitrile, ketones, such as: acetone, methyl ethyl ketone, diethyl ketone and third butyl methyl ketone, alcohols, such as: methanol, ethanol , n-propanol, isopropanol, n-butanol, tert-butanol, water and dimethyl hydrazine, dimethylformamide and dimethylacetamide, and morpholine and N-methylmorpholine. Mixtures of solvents such as those described above can also be used. It is preferred to use tetrahydrofuran.

醇II之脫水法係轉化醇官能基形成良好之脫離基，隨後類似先前技藝之已知製程進行消去反應，例如：類似Helv.Chim.Acta 1947,30,1454；Liebigs Ann.Chem 1992,(7),687－692,Carbanions.24."(E)－與(Z)－2,2－二苯基－3－戊烯基鹼金屬化合物之重組反應"；Sch.Chem.,Georgia Inst.Technol.、Atlanta,GA,USA；J.Org.Chem.1989,54(7),1671－1679；Chemical & Pharmaceutical Bulletin 1986,34(7),2786－2798說明之製程進行，其揭示內容已以引用方式完全併入本文中。The dehydration process of alcohol II converts the alcohol functional group to form a good debonding group, followed by elimination reactions similar to those known in the prior art, for example: similar to Helv. Chim. Acta 1947, 30, 1454; Liebigs Ann. Chem 1992, (7 ), 687-692, Carbanions.24. "Recombination reaction of (E)-(Z)-2,2-diphenyl-3-pentenyl alkali metal compound"; Sch.Chem.,Georgia Inst.Technol ., Atlanta, GA, USA; J. Org. Chem. 1989, 54(7), 1671-1679; Chemical & Pharmaceutical Bulletin 1986, 34(7), 2786-2798. The process is described, the disclosure of which has been incorporated by reference. The approach is fully incorporated herein.

A.2項第二項(A.2項)中，化合物I係由化合物II於合適脫水劑之存在下脫水後製成，如下列反應圖所示。In item A.2, item 2 (A.2), compound I is prepared by dehydrating compound II in the presence of a suitable dehydrating agent, as shown in the following reaction scheme.

合適脫水劑為例如：三苯基膦/DEAD(DEAD＝偶氮二羧酸二乙酯)與伯格斯試劑(Burgess reagent)系統。三苯基膦與DEAD之組合通常用於針對對掌性之經羥基取代之中心之轉化反應(米茲諾反應(Mitsunobu反應))；然而，若沒有親核物存在下，其即作為溫和脫水劑。以化合物II為基準計，該系統最好過量使用，其中三苯基膦與DEAD兩種成份宜呈約等莫耳比例。Suitable dehydrating agents are, for example, triphenylphosphine/DEAD (DEAD = diethyl azodicarboxylate) and the Burgess reagent system. The combination of triphenylphosphine and DEAD is typically used for the conversion reaction to the palm-substituted center of the palm (Mitsunobu reaction); however, if there is no nucleophile, it is used as a mild dehydration Agent. Preferably, the system is used in excess based on the compound II, wherein the triphenylphosphine and the DEAD are preferably present in an approximate molar ratio.

伯格斯試劑為兩性離子之N－(三乙基銨磺醯基胺甲酸酯((C2 H5 )3 N＋ －SO2 －N－ －COOCH3 )，係一種溫和脫水劑。以醇II為基準計，用量可為等莫耳量或超過莫耳量。其與伯格斯試劑之反應通常在惰性有機溶劑中進行。合適惰性有機溶劑包括芳香烴類，如：甲苯、鄰－、間與對－二甲苯，鹵化烴類，如：二氯甲烷、二氯乙烷、氯仿與氯苯，醚，如：***、二異丙基醚、第三丁基甲基醚、二烷、苯甲醚與四氫呋喃，腈類，如：乙腈與丙腈，與酮類，如：丙酮、甲基乙基酮、二乙基酮與第三丁基甲基酮。較佳為使用芳香烴類或其混合物，尤指甲苯。The Bourges reagent is a zwitterionic N-(triethylammonium sulfonylcarbamate ((C 2 H 5 ) 3 N + -SO 2 -N - -COOCH 3 ), a mild dehydrating agent. Alcohol II is used in an amount equal to or exceeding the molar amount. The reaction with the Burgers reagent is usually carried out in an inert organic solvent. Suitable inert organic solvents include aromatic hydrocarbons such as toluene, o- , m- and p-xylene, halogenated hydrocarbons such as: dichloromethane, dichloroethane, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, Alkanes, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, and ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone. It is preferred to use aromatic hydrocarbons or mixtures thereof, especially toluene.

醇II使用脫水劑之脫水法可類似先前技藝已知方法進行，例如：類似Synthesis 2003,201與J.Indian Sci.2001,81,461說明之方法，其揭示內容已以引用方式完全併入本文中。The dehydration of the alcohol II using a dehydrating agent can be carried out in a manner similar to that known in the prior art, for example, a method similar to that described in Synthesis 2003, 201 and J. Indian Sci. 2001, 81, 461, the disclosure of which is hereby incorporated by reference in its entirety.

製法BSystem B

製法A中兩項製程(A.1與A.2)所使用式II醇可例如：類似文獻中已知方法製備，其係由式IV之相應二肽前體環化，例如：類似T.Kawasaki等人之Org.Lett.2(19)(2000),3027－3029、Igor L.Rodionov等人之Tetrahedron 58(42)(2002),8515－8523或A.L.Johnson等人之Tetrahedron 60(2004),961－965說明之方法進行。下文中，式IV二肽形成醇II之環化法亦在下文中稱為製法B，其示於下列反應圖。The alcohol of formula II used in the two processes of Process A (A.1 and A.2) can be prepared, for example, by methods known in the literature, which are cyclized from the corresponding dipeptide precursor of Formula IV, for example: similar to T. Kawasaki et al., Org. Lett. 2 (19) (2000), 3027-3029, Igor L. Rodionov et al., Tetrahedron 58 (42) (2002), 8515-8523 or AL Johnson et al., Tetrahedron 60 (2004) The method described in 961-965 is carried out. Hereinafter, the cyclization method for forming the alcohol II of the dipeptide of the formula IV is also referred to as Process B below, which is shown in the following reaction scheme.

式IV中，代號A1 、A2 、R1 －R6 、Ra 、Rb 、Rc 、Rd 、Re 與Rf 如式I之定義。基團ORx 為利用氧附接之合適脫離基。此時，Rx 為例如：C1 －C6 －烷基，特定言之甲基或乙基，或苯基－C1 －C6 －烷基，例如：苯甲基。In Formula IV, the symbols A 1 , A 2 , R 1 - R 6 , R a , R b , R c , R d , R e and R f are as defined in Formula I. The group OR x is a suitable leaving group that is attached by oxygen. In this case, R x is, for example, a C 1 -C 6 -alkyl group, specifically a methyl group or an ethyl group, or a phenyl-C 1 -C 6 -alkyl group, for example, a benzyl group.

該環化反應可例如：由式IV二肽於酸或鹼之存在下進行(酸性或鹼性環化法)或加熱反應混合物進行(熱環化法)。The cyclization reaction can be carried out, for example, by carrying out the dipeptide of the formula IV in the presence of an acid or a base (acidic or basic cyclization) or by heating the reaction mixture (thermal cyclization).

加至二肽IV中之鹼類或酸類係呈等莫耳量或過量。根據本發明製法之特別具體實施例中，以肽為基準計，鹼或酸係使用過量。The base or acid added to the dipeptide IV is in an equivalent molar amount or excess. In a particular embodiment of the process of the invention, the base or acid is used in excess based on the peptide.

肽IV於鹼之存在下之反應通常在0℃至反應混合物沸點之溫度範圍內進行，較佳為10℃至50℃，特別佳為15℃至35℃。通常，該反應在溶劑中進行，較佳為在惰性有機溶劑中。The reaction of the peptide IV in the presence of a base is usually carried out at a temperature ranging from 0 ° C to the boiling point of the reaction mixture, preferably from 10 ° C to 50 ° C, particularly preferably from 15 ° C to 35 ° C. Usually, the reaction is carried out in a solvent, preferably in an inert organic solvent.

合適惰性有機溶劑包括脂系烴類，如：戊烷、己烷、環己烷及C5 －C8 －烷類之混合物，芳香烴類，如：甲苯、鄰－、間與對－二甲苯，鹵化烴類，如：二氯甲烷、二氯以烷、氯仿與氯苯，醚類，如：***、二異丙基醚、第三丁基甲基醚、二烷，苯甲醚與四氫呋喃，腈類，如：乙腈與丙腈，酮類，如：丙酮、甲基乙基酮、二乙基酮與第三丁基甲基酮，醇類，如：甲醇、乙醇、正丙醇、異丙醇、正丁醇、第三丁醇，水與二甲亞碸，二甲基甲醯胺與二甲基乙醯胺，及嗎啉與N－甲基嗎啉。亦可使用如上述溶劑之混合物。Suitable inert organic solvents include aliphatic hydrocarbons such as pentane, hexane, cyclohexane and mixtures of C 5 -C 8 -alkanes, aromatic hydrocarbons such as toluene, o-, m- and p-xylene , halogenated hydrocarbons, such as: dichloromethane, dichlorohexane, chloroform and chlorobenzene, ethers, such as: ether, diisopropyl ether, tert-butyl methyl ether, two Alkanes, anisole and tetrahydrofuran, nitriles, such as: acetonitrile and propionitrile, ketones, such as: acetone, methyl ethyl ketone, diethyl ketone and third butyl methyl ketone, alcohols, such as: methanol, ethanol , n-propanol, isopropanol, n-butanol, tert-butanol, water and dimethyl hydrazine, dimethylformamide and dimethylacetamide, and morpholine and N-methylmorpholine. Mixtures of solvents such as those described above can also be used.

本發明較佳具體實施例中，該反應係於四氫呋喃－水混合物中，例如：使用例如：1：10至10：1之混合比例(體積比)進行。In a preferred embodiment of the invention, the reaction is carried out in a tetrahydrofuran-water mixture, for example, using a mixing ratio (volume ratio) of, for example, 1:10 to 10:1.

通常合適鹼為無機化合物，如：鹼金屬與鹼土金屬氫氧化物，如：氫氧化鋰、氫氧化鈉、氫氧化鉀或氫氧化鈣、氨之水溶液、鹼金屬或鹼土金屬氧化物，如：氧化鋰、氧化鈉、氧化鈣與氧化鎂、鹼金屬與鹼土金屬氫化物，如：氫化鋰、氫化鈉、氫化鉀與氫化鈣、鹼金屬胺化物，如：胺化鋰，例如：二異丙基胺化鋰、胺化鈉與胺化鉀、鹼金屬與鹼土金屬碳酸鹽，如：碳酸鋰、碳酸鉀、碳酸銫與碳酸鈣，及鹼金屬碳酸氫鹽，如：碳酸氫鈉、有機金屬化合物，特定言之鹼金屬烷化物，如：甲基鋰、丁基鋰與苯基鋰、烷基鎂鹵化物，如：甲基鎂化氯，及鹼金屬與鹼土金屬醇鹽，如：甲醇鈉、乙醇鈉、乙醇鉀、第三丁醇鉀、第三戊醇鉀與二甲氧基鎂，及有機鹼類，例如：第三胺類，如：三甲基胺、三乙基胺、二異丙基乙基胺、2－羥基吡啶與N－甲基哌啶、吡啶、經取代之吡啶，如：三甲基吡啶、吡啶二羧酸與4－二甲基胺基吡啶，及雙環胺類。當然亦可使用不同鹼類之混合物。Generally, the suitable base is an inorganic compound such as an alkali metal and an alkaline earth metal hydroxide such as lithium hydroxide, sodium hydroxide, potassium hydroxide or calcium hydroxide, an aqueous solution of ammonia, an alkali metal or an alkaline earth metal oxide such as: Lithium oxide, sodium oxide, calcium oxide and magnesium oxide, alkali metal and alkaline earth metal hydride, such as: lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal amines, such as: lithium amination, such as: diisopropyl Lithium amide, sodium amination and potassium amination, alkali metal and alkaline earth metal carbonates, such as: lithium carbonate, potassium carbonate, cesium carbonate and calcium carbonate, and alkali metal hydrogencarbonates, such as: sodium hydrogencarbonate, organic metals a compound, in particular an alkali metal alkylate such as methyl lithium, butyl lithium and phenyl lithium, an alkyl magnesium halide such as methylmagnesium chloride, and an alkali metal and alkaline earth metal alkoxide such as methanol. Sodium, sodium ethoxide, potassium ethoxide, potassium butoxide, potassium pentaerythritol and magnesium dimethoxide, and organic bases, such as: tertiary amines such as trimethylamine, triethylamine, Diisopropylethylamine, 2-hydroxypyridine and N-methyl piperidine, pyridyl , The substituted pyridine, such as: collidine, pyridine dicarboxylic acid with 4-dimethylaminopyridine, and bicyclic amines. It is of course also possible to use mixtures of different bases.

根據本發明製法之具體實施例中，IV之反應係於鹼之存在下，較佳為於鹼類第三丁醇鉀、2－羥基吡啶或氨之水溶液或此等鹼類之混合物之存在下進行。較佳為僅使用其中一種鹼。特別佳具體實施例中，該反應係於氨之水溶液(例如：濃度10至50%(w/v))之存在下進行。In a specific embodiment of the process of the present invention, the reaction of IV is in the presence of a base, preferably in the presence of a solution of a base of potassium butoxide, a solution of 2-hydroxypyridine or ammonia or a mixture of such bases. get on. It is preferred to use only one of the bases. In a particularly preferred embodiment, the reaction is carried out in the presence of an aqueous solution of ammonia (e.g., a concentration of 10 to 50% (w/v)).

IV於酸之存在下之反應通常在10℃至反應混合物之沸點之溫度範圍內進行，較佳為50℃至沸點，特別佳為在回流之沸點下進行。通常，該反應在溶劑中，較佳為在惰性有機溶劑中進行。The reaction of IV in the presence of an acid is usually carried out at a temperature ranging from 10 ° C to the boiling point of the reaction mixture, preferably from 50 ° C to the boiling point, particularly preferably at the boiling point of reflux. Usually, the reaction is carried out in a solvent, preferably in an inert organic solvent.

原則上，合適溶劑為彼等亦可用於鹼性環化反應之溶劑，特定言之醇類。較佳具體實施例中，該反應係於正丁醇中進行。In principle, suitable solvents are those which can also be used in the basic cyclization reaction, in particular alcohols. In a preferred embodiment, the reaction is carried out in n-butanol.

原則上，適合IV之環化反應之酸類為伯忍斯特(Brnstedt)酸與路易士(Lewis)酸。特定言之，可使用無機酸，例如：氫鹵酸，如：氫氟酸、鹽酸、氫溴酸、無機氧代酸類，如：硫酸與過氯酸，及其他無機路易士酸類，如：三氟化硼、三氯化鋁、氯化鐵(III)、氯化錫(IV)、氯化鈦(IV)與氯化鋅(II)，及有機酸類，例如：羧酸類與羥基羧酸類，如：甲酸、乙酸、丙酸、草酸、檸檬酸與三氟乙酸，及有機磺酸類，如：甲苯磺酸、苯磺酸、樟腦磺酸，等等。亦可使用不同酸類之混合物。In principle, the acid suitable for the cyclization reaction of IV is Burrester (Br Nstedt) acid with Lewis acid. In particular, inorganic acids can be used, such as: hydrohalic acids, such as: hydrofluoric acid, hydrochloric acid, hydrobromic acid, inorganic oxo acids, such as: sulfuric acid and perchloric acid, and other inorganic Lewis acids, such as: Boron fluoride, aluminum trichloride, iron (III) chloride, tin (IV) chloride, titanium (IV) chloride and zinc (II) chloride, and organic acids such as carboxylic acids and hydroxycarboxylic acids, For example: formic acid, acetic acid, propionic acid, oxalic acid, citric acid and trifluoroacetic acid, and organic sulfonic acids, such as: toluenesulfonic acid, benzenesulfonic acid, camphorsulfonic acid, and the like. Mixtures of different acids can also be used.

根據本發明製法具體實施例中，該反應係於有機酸之存在下進行，例如：於羧酸之存在下，如：甲酸、乙酸或三氟乙酸或此等酸類之混合物。最好僅使用其中一種酸。較佳具體實施例中，該反應係於乙酸中進行。According to a particular embodiment of the process of the invention, the reaction is carried out in the presence of an organic acid, for example in the presence of a carboxylic acid such as formic acid, acetic acid or trifluoroacetic acid or a mixture of such acids. It is best to use only one of the acids. In a preferred embodiment, the reaction is carried out in acetic acid.

酸性環化反應之特別佳具體實施例係於正丁醇、N－甲基嗎啉與乙酸之存在下，於回流條件下進行。A particularly preferred embodiment of the acid cyclization reaction is carried out under reflux conditions in the presence of n-butanol, N-methylmorpholine and acetic acid.

本發明其他具體實施例中，該反應僅加熱反應混合物(熱環化法)。此時，該反應通常在10℃至該反應混合物之沸點之溫度範圍內進行，較佳為50℃至該反應混合物之沸點，特別佳為在該反應混合物之回流沸點下進行。通常，該反應係在溶劑中進行，較佳為在惰性有機溶劑中進行。In other embodiments of the invention, the reaction only heats the reaction mixture (thermal cyclization). At this time, the reaction is usually carried out at a temperature ranging from 10 ° C to the boiling point of the reaction mixture, preferably from 50 ° C to the boiling point of the reaction mixture, particularly preferably at the reflux boiling point of the reaction mixture. Usually, the reaction is carried out in a solvent, preferably in an inert organic solvent.

原則上，合適溶劑為彼等用於鹼性環化法之溶劑。較佳為極性非質子性溶劑，例如：二甲亞碸或二甲基甲醯胺或其混合物。較佳具體實施例中，該反應係在二甲亞碸中進行。In principle, suitable solvents are those which are used in the basic cyclization process. Preferred are polar aprotic solvents such as dimethyl hydrazine or dimethylformamide or mixtures thereof. In a preferred embodiment, the reaction is carried out in dimethyl hydrazine.

製法B所得之該反應混合物，及製法A.1與A.2與下文說明製程所得反應混合物均可依習知方式操作。其作法為例如：與水混合，分相且若適當時，由粗產物經層析法純化。有些中間物與終產物係呈黏狀油得到，其通常再經純化或於減壓及適度加溫下排除揮發性成份。若所得中間物與終產物呈固體時，該純化法則採用再結晶或煮解法進行。The reaction mixture obtained in Process B, and the reaction mixtures obtained in Processes A.1 and A.2 and the processes described below can be operated in a conventional manner. This is carried out, for example, by mixing with water, phase separation and, if appropriate, purification of the crude product by chromatography. Some intermediates are obtained as a viscous oil from the final product, which is usually purified or subjected to vacuum and moderate warming to exclude volatile components. If the resulting intermediate is solid as the final product, the purification is carried out by recrystallization or digestion.

製備式II化合物時所需之部份前體與中間物可自商品取得、自文獻中已知或可依文獻中已知方法製備。Some of the precursors and intermediates required for the preparation of the compound of formula II are commercially available, known from the literature or can be prepared by methods known in the literature.

二肽式IV可例如：由通式V之N－受保護之二肽類似文獻中已知方法製備，例如：依據Glenn L.Stahl等人之J.Org.Chem.43(11),(1978),2285－6或A.K.Ghosh et al.,Org.Lett.3(4),(2001),635－638說明之方法。Dipeptides of Formula IV can be prepared, for example, from N-protected dipeptides of Formula V analogously to methods known in the literature, for example, according to Glenn L. Stahl et al., J. Org. Chem. 43 (11), (1978). ), 2285-6 or AKGhosh et al., Org. Lett. 3 (4), (2001), 635-638.

式IV與V中，代號A1 、A2 、R1 －R6 、Ra 、Rb 、Rc 、Rd 、Re 與Rf 如式I之定義，SG為氮保護基，如：Boc(＝第三丁氧基羰基)，ORx 為利用氧原子附接之脫離基。當然，式II化合物之各較佳定義亦同樣適用於式IV或V化合物。如上述與脫離基ORx 相關之說明亦適用於式IV二肽。In formulae IV and V, the codes A 1 , A 2 , R 1 - R 6 , R a , R b , R c , R d , R e and R f are as defined in formula I, and SG is a nitrogen protecting group, such as: Boc (=t-butoxycarbonyl), OR x is a leaving group attached by an oxygen atom. Of course, the preferred definitions of the compounds of formula II are equally applicable to the compounds of formula IV or V. The description relating to the detachment group OR x as described above also applies to the dipeptide of the formula IV.

因此例如：式V中SG為Boc與ORx 為合適脫離基，其中Rx 為例如：C1 －C6 －烷基，特定言之甲基、乙基或苯甲基之二肽可於酸之存在下轉化成式IV化合物。Thus, for example, in the formula V, SG is Boc and OR x is a suitable leaving group, wherein R x is, for example, a C 1 -C 6 -alkyl group, in particular a methyl, ethyl or benzyl dipeptide can be used in the acid Conversion to a compound of formula IV in the presence of it.

該反應通常在－30℃至該反應混合物之沸點之範圍內進行，較佳為0℃至50℃，特別佳為20℃至35℃。The reaction is usually carried out at a temperature ranging from -30 ° C to the boiling point of the reaction mixture, preferably from 0 ° C to 50 ° C, particularly preferably from 20 ° C to 35 ° C.

該反應可在溶劑中進行，特定言之在惰性有機溶劑中進行。合適溶劑原則上為鹼性環化法中所提之化合物，特定言之四氫呋喃或二氯甲烷或其混合物。較佳具體實施例中，該反應係在二氯甲烷中進行。The reaction can be carried out in a solvent, in particular in an inert organic solvent. Suitable solvents are in principle the compounds mentioned in the basic cyclization process, in particular tetrahydrofuran or dichloromethane or mixtures thereof. In a preferred embodiment, the reaction is carried out in dichloromethane.

所使用之酸類為二肽IV形成哌II之環化法所提及之酸類。The acid used is dipeptide IV forming a pipe The acid mentioned in the cyclization method of II.

根據本發明製法之一項具體實施例中，該反應係於有機酸類之存在下，例如：於強有機酸之存在下，如：甲酸、乙酸或三氟乙酸或其混合物進行。較佳具體實施例中，該反應係在三氟乙酸之存在下進行。According to a particular embodiment of the process of the invention, the reaction is carried out in the presence of an organic acid, for example in the presence of a strong organic acid, such as formic acid, acetic acid or trifluoroacetic acid or a mixture thereof. In a preferred embodiment, the reaction is carried out in the presence of trifluoroacetic acid.

該操作法可類似二肽IV形成哌II之環化法之說明進行。This method can be similar to dipeptide IV to form a pipe The description of the cyclization method of II is carried out.

式V之受保護之二肽可類似文獻中已知方法製備，例如：依據Wilford L.Mendelson等人之Int.J.Peptide & Protein Research 35(3),(1990),249－57說明之方法。典型途徑為使用式VII胺基酸酯與Boc－保護之胺基酸VI進行醯胺化反應，如下列反應圖所示： Protected dipeptides of formula V can be prepared analogously to methods known in the literature, for example, according to the method described by Wilford L. Mendelson et al., Int. J. Peptide & Protein Research 35 (3), (1990), 249-57. . A typical route is to carry out a guanidation reaction with a Boc-protected amino acid VI using an amino acid ester of formula VII, as shown in the following reaction scheme:

此反應圖中，其代號如上述定義。除了Boc外，亦可改用其他胺基保護基替代。In this reaction diagram, the code is as defined above. In addition to Boc, other amine-based protecting groups can be used instead.

通常，VII與VI之反應係於－30℃至該反應混合物之沸點之溫度範圍進行，較佳為0℃至50℃，特別佳為20℃至35℃。該反應可在溶劑中進行，最好在惰性有機溶劑中進行。合適溶劑為IV形成II之鹼性環化法所述及之溶劑。Usually, the reaction of VII with VI is carried out at a temperature ranging from -30 ° C to the boiling point of the reaction mixture, preferably from 0 ° C to 50 ° C, particularly preferably from 20 ° C to 35 ° C. The reaction can be carried out in a solvent, preferably in an inert organic solvent. A suitable solvent is the solvent described in the basic cyclization method of IV forming II.

通常，該反應需要活化劑之存在。合適活化劑為縮合劑，如，例如：聚苯乙烯－或非聚苯乙烯－承載之二環己基碳化二亞胺(DCC)、二異丙基碳化二亞胺、1－乙基－3－(二甲基胺基丙基)碳化二亞胺(EDAC)、羰基二咪唑、氯甲酸酯類，如：氯甲酸甲酯、氯甲酸乙酯、氯甲酸異丙酯、氯甲酸異丁酯、氯甲酸第二丁酯或氯甲酸烯丙酯、特戊烯氯、聚磷酸、丙膦酸酐、雙(2－氧代－3－唑啶基)－磷醯氯(BOPCl)或磺醯氯，如：甲磺醯氯、甲苯磺醯氯或苯磺醯氯。依據一項具體實施例，較佳活化劑為EDAC或DCC。Typically, this reaction requires the presence of an activating agent. Suitable activators are condensing agents such as, for example, polystyrene- or non-polystyrene-supported dicyclohexylcarbodiimide (DCC), diisopropylcarbodiimide, 1-ethyl-3- (Dimethylaminopropyl)carbodiimide (EDAC), carbonyldiimidazole, chloroformate, such as methyl chloroformate, ethyl chloroformate, isopropyl chloroformate, isobutyl chloroformate, Dibutyl chloroformate or allyl chloroformate, pentene chloride, polyphosphoric acid, phosphinic anhydride, bis(2-oxo-3- Zoxazinyl)-phosphonium chloride (BOPCl) or sulfonium chloride, such as: methanesulfonium chloride, toluenesulfonium chloride or benzenesulfonyl chloride. According to a specific embodiment, the preferred activator is EDAC or DCC.

VII與VI之反應最好在鹼之存在下進行。合適鹼類為二肽IV形成哌II之環化法所提及之鹼類。一項具體實施例中，所使用之鹼類為三乙基胺或N－乙基二異丙基胺或其混合物，特別佳為N－乙基二異丙基胺。The reaction of VII with VI is preferably carried out in the presence of a base. Suitable bases are dipeptide IV to form a pipe The bases mentioned in the cyclization method of II. In a particular embodiment, the base used is triethylamine or N-ethyldiisopropylamine or a mixture thereof, particularly preferably N-ethyldiisopropylamine.

該操作法係類似二肽IV形成哌II之環化法進行。This method is similar to dipeptide IV forming a pipe The cyclization method of II is carried out.

此部份之式VII化合物可脫除相應之受保護之胺基酸化合物VIII之保護基製備，其係類似文獻中已知方法，例如：依據Glenn L.Stahl等人之J.Org.Chem.43(11),(1978),2285－6或A.K.Ghosh等人之Org.Lett.3(4),(2001),635－638說明之方法進行。由Boc－保護之胺基酸化合物VIII製備VII之方法示於下列反應圖。This portion of the compound of formula VII can be prepared by removal of the protecting group of the corresponding protected amino acid compound VIII, which is analogous to methods known in the literature, for example, according to Glenn L. Stahl et al., J. Org. Chem. The method described in 43 (11), (1978), 2285-6 or AK Ghosh et al., Org. Lett. 3 (4), (2001), 635-638. The process for the preparation of VII from Boc-protected amino acid compound VIII is shown in the following reaction scheme.

此反應圖中，代號如上述定義。除了Boc外，亦可改用其他胺基保護基替代。In this reaction diagram, the code is as defined above. In addition to Boc, other amine-based protecting groups can be used instead.

式VIII化合物形成化合物VII之轉化法典型係於酸之存在下，於－30℃至該反應混合物之沸點之範圍內進行，較佳為0℃至50℃，特別佳為20℃至35℃。該反應可在溶劑中進行，較佳為在惰性有機溶劑中進行。The conversion of the compound of the formula VIII to the compound VII is typically carried out in the presence of an acid in the range of from -30 ° C to the boiling point of the reaction mixture, preferably from 0 ° C to 50 ° C, particularly preferably from 20 ° C to 35 ° C. The reaction can be carried out in a solvent, preferably in an inert organic solvent.

合適溶劑原則上為鹼性環化法述及之溶劑。特定言之，四氫呋喃或二氯甲烷或其混合物。較佳具體實施例中，該反應在二氯甲烷中進行。Suitable solvents are in principle the solvents mentioned in the basic cyclization process. Specifically, tetrahydrofuran or dichloromethane or a mixture thereof. In a preferred embodiment, the reaction is carried out in dichloromethane.

所使用之酸類與酸性觸媒為二肽IV形成哌II之環化法所提及之化合物。The acid used and the acidic catalyst form a dipeptide IV to form a pipe The compound mentioned in the cyclization method of II.

根據本發明製法之一項具體實施例中，該反應係在有機酸之存在下進行，例如：於強有機酸之存在下，如：甲酸、乙酸或三氟乙酸或其混合物。較佳具體實施例中，該反應係在三氟乙酸之存在下進行。According to a particular embodiment of the process of the invention, the reaction is carried out in the presence of an organic acid, for example in the presence of a strong organic acid such as formic acid, acetic acid or trifluoroacetic acid or a mixture thereof. In a preferred embodiment, the reaction is carried out in the presence of trifluoroacetic acid.

該操作法係類似二肽IV形成哌II之環化法所說明之方法進行。This method is similar to dipeptide IV forming a pipe The method described in the cyclization method of II is carried out.

式VIII化合物可依據下列反應圖所示反應製備。化合物XI與受保護之胺基酸化合物X之反應可類似文獻中已知方法進行，例如：依據I.Ojima等人之J.Am.Chem.Soc.,109(21),(1987),6537－6538或J.M.McIntosh等人之Tetrahedron 48(30),(1992),6219－6224。The compound of formula VIII can be prepared by reaction as shown in the following reaction scheme. The reaction of Compound XI with the protected amino acid compound X can be carried out analogously to methods known in the literature, for example according to I. Ojima et al., J. Am. Chem. Soc., 109 (21), (1987), 6537. -6538 or J. Chem Intosh et al., Tetrahedron 48 (30), (1992), 6219-6224.

此反應圖中，代號如上述定義。L為脫離基。除了Boc外，亦可改用其他胺基保護基替代。In this reaction diagram, the code is as defined above. L is a leaving group. In addition to Boc, other amine-based protecting groups can be used instead.

XI與X之反應通常在鹼之存在下進行。合適鹼類為二肽IV形成哌II之環化法所提及之化合物。其他較佳具體實施例中，所使用之鹼為二異丙基胺化鋰，特別佳為實質上等莫耳量，特定言之等莫耳量。The reaction of XI with X is usually carried out in the presence of a base. Suitable bases are dipeptide IV to form a pipe The compound mentioned in the cyclization method of II. In other preferred embodiments, the base used is lithium diisopropylamide, particularly preferably substantially equal to the molar amount, in particular the molar amount.

通常，該反應在－78℃至該反應混合物之沸點之範圍內進行，較佳為－78℃至沸點，特別佳為－78℃至30℃。Usually, the reaction is carried out at a temperature ranging from -78 ° C to the boiling point of the reaction mixture, preferably from -78 ° C to the boiling point, particularly preferably from -78 ° C to 30 ° C.

該反應可在溶劑中進行，較佳為在惰性有機溶劑中進行。合適溶劑原則上為鹼性環化法所述及之溶劑，特定言之二氯甲烷或四氫呋喃或其混合物。較佳具體實施例中，該反應係在四氫呋喃中進行。The reaction can be carried out in a solvent, preferably in an inert organic solvent. Suitable solvents are, in principle, the solvents mentioned in the basic cyclization process, in particular dichloromethane or tetrahydrofuran or mixtures thereof. In a preferred embodiment, the reaction is carried out in tetrahydrofuran.

該操作法係類似二肽IV形成哌II之環化法所說明之方法進行。This method is similar to dipeptide IV forming a pipe The method described in the cyclization method of II is carried out.

有些式XI化合物可自商品取得或可由自商品取得之相應前體，依文獻中說明之轉形法製備。Some of the compounds of formula XI can be obtained from commercial products or can be prepared from the corresponding precursors obtained from the commercial products according to the transformation method described in the literature.

製法CMethod C

式II.1中R3 為H之化合物亦可於醛醇反應中，由醛XII與哌XIII偶合製得，其示於下列反應圖： The compound of formula II.1 wherein R 3 is H may also be used in the aldol reaction from aldehyde XII and piperidine. XIII is prepared by coupling, which is shown in the following reaction chart:

式II.1、XII與XIII中，代號A1 、A2 、R1 －R6 、Ra 、Rb 、Rc 、Rd 、Re 與Rf 如式I之定義。In the formulae II.1, XII and XIII, the symbols A 1 , A 2 , R 1 - R 6 , R a , R b , R c , R d , R e and R f are as defined in the formula I.

該反應通常係於合適鹼類之存在下進行。合適鹼類為一般用於醛醇反應之鹼類。其實例為IV形成II之環化法所述及之化合物。較佳為使用鹼金屬胺化物，如：二異丙基胺化鋰。合適反應條件係先前技藝習知者，且說明於例如：J.Org.Chem.2000,65(24),8402－8405，其揭示內容已以引用方式完全併入本文中。This reaction is usually carried out in the presence of a suitable base. Suitable bases are the bases commonly used in the aldol reaction. An example of this is the compound described by IV to form the cyclization method of II. It is preferred to use an alkali metal amide such as lithium diisopropylamide. Suitable reaction conditions are well known to those skilled in the art and are described, for example, in J. Org. Chem. 2000, 65(24), 8402-8405, the disclosure of which is hereby incorporated by reference.

醛醇反應可直接產生相應醛醇縮合反應產物，亦即式I.1中R3 為H之化合物。特別當該反應在加溫下且反應時間相當長下進行時。The aldol reaction directly produces the corresponding aldol reaction product, i.e., the compound of formula I.1 wherein R 3 is H. This is especially the case when the reaction is carried out under heating and the reaction time is rather long.

醛XII為自商品取得或可依據醛之已知製法製備。此等醛醇縮合反應可類似J.Org.Chem.2000,65(24),8402－8405說明之製法進行，其揭示內容已以引用方式併入本文中。The aldehyde XII is prepared from a commercial product or can be prepared according to a known method for preparing an aldehyde. Such aldol condensation reactions can be carried out analogously to the processes described in J. Org. Chem. 2000, 65(24), 8402-8405, the disclosure of which is incorporated herein by reference.

原則上，醛醇反應或縮合反應亦可用於製備化合物I，其中R3 不一定為氫，但亦可為C1 －C6 －烷基、C3 －C6 －環烷基、C2 －C6 －烯基、C3 －C6 －環烯基、C2 －C6 －炔基、C3 －C6 －環炔基、苯基、苯基－(C1 －C6 )－烷基、雜環基、雜環基－(C1 －C6 )－烷基；苯基－[C1 －C6 －烷氧基羰基]－(C1 －C6 )－烷基或苯基雜環基－(C1 －C6 )－烷基，尤指C1 －C6 －烷基。此時，可改用酮IX替代醛XII， 其中R3 為C1 －C6 －烷基、C3 －C6 －環烷基、C2 －C6 －烯基、C3 －C6 －環烯基、C2 －C6 －炔基、C3 －C6 －環炔基、苯基、苯基－(C1 －C6 )－烷基、雜環基、雜環基－(C1 －C6 )－烷基；苯基－[C1 －C6 －烷氧基羰基]－(C1 －C6 )－烷基或苯基雜環基－(C1 －C6 )－烷基，尤指C1 －C6 －烷基。In principle, an aldol reaction or a condensation reaction can also be used to prepare compound I, wherein R 3 is not necessarily hydrogen, but can also be C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 2 - C 6 -alkenyl, C 3 -C 6 -cycloalkenyl, C 2 -C 6 -alkynyl, C 3 -C 6 -cycloalkynyl, phenyl, phenyl-(C 1 -C 6 )-alkane , heterocyclic, heterocyclyl-(C 1 -C 6 )-alkyl; phenyl-[C 1 -C 6 -alkoxycarbonyl]-(C 1 -C 6 )-alkyl or phenyl Heterocyclyl-(C 1 -C 6 )-alkyl, especially C 1 -C 6 -alkyl. At this point, you can use ketone IX instead of aldehyde XII. Wherein R 3 is C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 2 -C 6 -alkenyl, C 3 -C 6 -cycloalkenyl, C 2 -C 6 -alkynyl , C 3 -C 6 -cycloalkynyl, phenyl, phenyl-(C 1 -C 6 )-alkyl, heterocyclic, heterocyclyl-(C 1 -C 6 )-alkyl; phenyl- [C 1 -C 6 -alkoxycarbonyl]-(C 1 -C 6 )-alkyl or phenylheterocyclyl-(C 1 -C 6 )-alkyl, especially C 1 -C 6 -alkane base.

然而，可能形成複雜之反應混合物，特定言之當R3 為其中附接在附接點之α－位置上之碳原子帶有一氫原子之基團時。此外，大多數例子中需要更強烈之反應條件，以便優先進行醛醇反應來製備化合物I.1。However, it is possible to form a complicated reaction mixture, in particular when R 3 is a group in which a carbon atom attached to the α-position of the attachment point carries a hydrogen atom. In addition, in most cases, more intense reaction conditions are required in order to preferentially carry out the aldol reaction to prepare compound I.1.

式XIII化合物可類似文獻中已知方法，由通式XIV化合物進行分子內環化法製備，例如：依據T.Kawasaki等人之Org.Lett.2(19)(2000),3027－3029,Igor L.Rodionov等人之Tetrahedron 58(42)(2002),8515－8523或A.L.Johnson等人之Tetrahedron 60(2004),961－965說明之方法。Compounds of formula XIII can be prepared by intramolecular cyclization from compounds of formula XIV, analogous to methods known in the literature, for example, according to T. Kawasaki et al., Org. Lett. 2 (19) (2000), 3027-3029, Igor The method described by L. Rodionov et al., Tetrahedron 58 (42) (2002), 8515-8523 or AL Johnson et al., Tetrahedron 60 (2004), 961-965.

式XIV中，代號Rx 、A2 、R1 、R2 、R4 、R5 、R6 、Rd 、Re 與Rf 如上述式IV之定義。基團ORx 為利氧附接之合適脫離基。此時，Rx 為例如：C1 －C6 －烷基，特定言之甲基或乙基，或苯基－C1 －C6 －烷基，例如：苯甲基。In the formula XIV, the symbols R x , A 2 , R 1 , R 2 , R 4 , R 5 , R 6 , R d , R e and R f are as defined in the above formula IV. The group OR x is a suitable leaving group for oxygen attachment. In this case, R x is, for example, a C 1 -C 6 -alkyl group, specifically a methyl group or an ethyl group, or a phenyl-C 1 -C 6 -alkyl group, for example, a benzyl group.

式XIV化合物之環化法可於鹼之存在下進行。此時，該反應通常在0℃至該反應混合物之沸點之溫度範圍內進行，較佳為10℃至50℃，特別佳為15℃至35℃。該反應可在溶劑中進行，較佳為在惰性有機溶劑中進行。The cyclization of the compound of formula XIV can be carried out in the presence of a base. At this time, the reaction is usually carried out at a temperature ranging from 0 ° C to the boiling point of the reaction mixture, preferably from 10 ° C to 50 ° C, particularly preferably from 15 ° C to 35 ° C. The reaction can be carried out in a solvent, preferably in an inert organic solvent.

合適溶劑原則上為熱環化法所述及之化合物，特定言之混合比例在1：10至10：1之四呋喃－水混合物。Suitable solvents are, in principle, the compounds described in the thermal cyclization process, in particular a mixture of tetrafuran-water in a ratio of 1:10 to 10:1.

合適鹼類為IV形成II之鹼性環化法(製法B)述及之鹼類。特定言之第三丁醇鉀、2－羥基吡啶或氨之水溶液或此等鹼類之混合物。較佳為僅使用其中一種鹼類。特別佳具體實施例中，該反應係在氨之水溶液(例如：濃度可為10至50%(w/v))之存在下進行。Suitable bases are the bases described in the basic cyclization method of IV formation II (Process B). A particular aqueous solution of potassium t-butoxide, 2-hydroxypyridine or ammonia or a mixture of such bases. It is preferred to use only one of the bases. In a particularly preferred embodiment, the reaction is carried out in the presence of an aqueous ammonia solution (e.g., a concentration of 10 to 50% (w/v)).

此部份之式XIV可依下列反應圖，類似文獻已知之方法，例如：依據Wilford L.Mendelson等人之Int.J.Peptide & Protein Research 35(3),(1990),249－57,Glenn L.Stahl等人之J.Org.Chem.43(11),(1978),2285－6或A.K.Ghosh等人之Org.Lett.3(4),(2001),635－638說明之方法製備。The formula XIV of this part can be based on the following reaction schemes, similar to those known in the literature, for example, according to Wilford L. Mendelson et al., Int. J. Peptide & Protein Research 35 (3), (1990), 249-57, Glenn. Preparation by L. Stahl et al., J. Org. Chem. 43 (11), (1978), 2285-6 or AK Ghosh et al., Org. Lett. 3 (4), (2001), 635-638. .

反應圖中，代號Rx 、A2 、R1 、R2 、R4 、R5 、R6 、Rd 、Re 與Rf 如上述式IV或XIV之定義。第一個步驟中，該合成法包括由胺基酸化合物XV與Boc－保護之胺基酸VI，於活化劑之存在下偶合。除了Boc外，亦可改用其他胺基保護基替代。In the reaction scheme, the symbols R x , A 2 , R 1 , R 2 , R 4 , R 5 , R 6 , R d , R e and R f are as defined in the above formula IV or XIV. In the first step, the synthesis involves coupling an amino acid compound XV with a Boc-protected amino acid VI in the presence of an activating agent. In addition to Boc, other amine-based protecting groups can be used instead.

式XV化合物與式VI化合物之反應通常在－30℃至該反應混合物之沸點之溫度範圍內進行，較佳為0℃至50℃，特別佳為20℃至35℃。該反應可在溶劑中進行，較佳為在惰性有機溶劑中進行。有關進一步說明可參見胺基酸化合物VI與化合物VII之醯胺化反應製備化合物V之方法。The reaction of the compound of the formula XV with the compound of the formula VI is usually carried out at a temperature ranging from -30 ° C to the boiling point of the reaction mixture, preferably from 0 ° C to 50 ° C, particularly preferably from 20 ° C to 35 ° C. The reaction can be carried out in a solvent, preferably in an inert organic solvent. For further explanation, reference may be made to the method for preparing compound V by the amidation reaction of amino acid compound VI with compound VII.

通常，該反應需要活化劑之存在。合適活化劑為縮合劑，如，例如：聚苯乙烯－或非聚苯乙烯－承載之二環己基碳化二亞胺(DCC)、二異丙基碳化二亞胺、1－乙基－3－(二甲基胺基丙基)碳化二亞胺(EDAC)、羰基二咪唑、氯甲酸酯類，如：氯甲酸甲酯、氯甲酸乙酯、氯甲酸異丙酯、氯甲酸丁酯、氯甲酸第二丁酯或氯甲酸烯丙酯、特戊烯氯、聚磷酸、丙膦酸酐、雙(2－氧代－3－唑啶基)－磷醯氯(BOPCl)或磺醯氯，如：甲磺醯氯、甲苯磺醯氯或苯磺醯氯。依據一項具體實施例，較佳活化劑為EDAC或DCC。Typically, this reaction requires the presence of an activating agent. Suitable activators are condensing agents such as, for example, polystyrene- or non-polystyrene-supported dicyclohexylcarbodiimide (DCC), diisopropylcarbodiimide, 1-ethyl-3- (Dimethylaminopropyl)carbodiimide (EDAC), carbonyldiimidazole, chloroformate, such as: methyl chloroformate, ethyl chloroformate, isopropyl chloroformate, butyl chloroformate, chlorine Dibutyl formate or allyl chloroformate, pentene chloride, polyphosphoric acid, phosphinic anhydride, bis(2-oxo-3- Zoxazinyl)-phosphonium chloride (BOPCl) or sulfonium chloride, such as: methanesulfonium chloride, toluenesulfonium chloride or benzenesulfonyl chloride. According to a specific embodiment, the preferred activator is EDAC or DCC.

XV與VI之反應最好在鹼之存在下進行。合適鹼類為製法B(二肽IV形成哌II之環化法)所述及之化合物。一項具體實施例中，所使用之鹼為三乙基胺或N－乙基二異丙基胺或其混合物，特別佳為N－乙基二異丙基胺。The reaction of XV with VI is preferably carried out in the presence of a base. The suitable base is Process B (dipeptide IV forms a pipe The compound described in the cyclization method of II). In a particular embodiment, the base used is triethylamine or N-ethyldiisopropylamine or a mixture thereof, particularly preferably N-ethyldiisopropylamine.

該操作法係類似製法B(二肽IV形成哌II之環化法)說明之方法進行。This method of operation is similar to Process B (dipeptide IV formation of piperidine) The method of cyclization of II) is carried out.

化合物XVI脫除保護基形成化合物XIV之方法典型地係在酸處理下進行。該反應通常在－30℃至該反應混合物之沸點之溫度範圍內進行，較佳為0℃至50℃，特別佳為20℃至35℃。該反應可在溶劑中進行，較佳為在惰性有機溶劑中進行。Removal of the protecting group from compound XVI The method of forming compound XIV is typically carried out under acid treatment. The reaction is usually carried out at a temperature ranging from -30 ° C to the boiling point of the reaction mixture, preferably from 0 ° C to 50 ° C, particularly preferably from 20 ° C to 35 ° C. The reaction can be carried out in a solvent, preferably in an inert organic solvent.

合適溶劑原則上為製法B中鹼性環化法所述及之溶劑，特定言之四氫呋喃或二氯甲烷或其混合物。較佳具體實施例中，該反應在二氯甲烷中進行。Suitable solvents are, in principle, the solvents described in the basic cyclization process of Process B, in particular tetrahydrofuran or dichloromethane or mixtures thereof. In a preferred embodiment, the reaction is carried out in dichloromethane.

所使用之酸為製法B(二肽IV形成哌II之環化法)所述及之酸類。有關進一步說明可參見V脫除保護基形成化合物IV之方法。其中所述及之反應條件亦適用於脫除化合物XVI之保護基。根據本發明製法之一項具體實施例中，該反應係於有機酸之存在下進行，特定言之強有機酸，例如：於甲酸、乙酸或三氟乙酸或其混合物之存在下進行。較佳具體實施例中，該反應係於三氟乙酸之存在下進行。The acid used is Process B (dipeptide IV forms a pipe The acid described in the cyclization method of II). For further explanation, reference may be made to the method of V-removing protecting groups to form compound IV. The reaction conditions described therein also apply to the removal of the protecting group of compound XVI. According to a particular embodiment of the process of the invention, the reaction is carried out in the presence of an organic acid, in particular a strong organic acid, for example in the presence of formic acid, acetic acid or trifluoroacetic acid or a mixture thereof. In a preferred embodiment, the reaction is carried out in the presence of trifluoroacetic acid.

若改用不同保護基替代Boc時，所採用之脫除保護基法當然需適合該保護基。If a different protecting group is used instead of Boc, the deprotecting method used is of course suitable for the protecting group.

操作法係類似製法B(二肽IV形成哌II之環化法)說明之方法進行。The operating method is similar to the preparation method B (dipeptide IV formation of piperidine The method of cyclization of II) is carried out.

製法DMethod D

本發明進一步提供一種製備通式I哌化合物之方法，其包括在鹼之存在下，由式IX化合物 其中代號A1 、Ra 、Rb 與Rc 如上述定義，R3 為氫、C1 －C6 －烷基、C3 －C6 －環烷基、C2 －C6 －烯基、C3 －C6 －環烯基、C2 －C6 －炔基、C3 －C6 －環炔基、苯基、苯基－(C1 －C6 )－烷基、雜環基、雜環基－(C1 －C6 )－烷基、苯基－[C1 －C6 －烷氧基羰基]－(C1 －C6 )－烷基或苯基雜環基－(C1 －C6 )－烷基，與式XVII膦酸酯反應 其中代號A2 、R1 、R2 、R4 、R5 、R6 、Rd 、Re 與Rf 如上述定義，Ry 為C1 －C4 －烷基，例如：甲基、乙基、丙基、異丙基、丁基或異丁基，芳基，例如：苯基，或芳基－C1 －C4 －烷基，例如：苯甲基。The invention further provides a preparation of the formula I a method of a compound comprising a compound of formula IX in the presence of a base Wherein the codes A 1 , R a , R b and R c are as defined above, and R 3 is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 2 -C 6 -alkenyl, C 3 -C 6 -cycloalkenyl, C 2 -C 6 -alkynyl, C 3 -C 6 -cycloalkynyl, phenyl, phenyl-(C 1 -C 6 )-alkyl, heterocyclic, Heterocyclyl-(C 1 -C 6 )-alkyl, phenyl-[C 1 -C 6 -alkoxycarbonyl]-(C 1 -C 6 )-alkyl or phenylheterocyclyl-(C 1 -C 6 )-alkyl, reacted with a phosphonate of formula XVII Wherein the codes A 2 , R 1 , R 2 , R 4 , R 5 , R 6 , R d , R e and R f are as defined above, and R y is C 1 -C 4 -alkyl, for example: methyl, B Base, propyl, isopropyl, butyl or isobutyl, aryl, for example phenyl, or aryl-C 1 -C 4 -alkyl, for example benzyl.

如上述反應亦可稱為威特－豪尼－艾蒙斯(Wittig－Horner－Emmons)反應。The above reaction can also be referred to as the Wittig-Horner-Emmons reaction.

Ry 較佳為C1 －C4 －烷基，特定言之甲基或乙基。R y is preferably a C 1 -C 4 -alkyl group, specifically a methyl group or an ethyl group.

此製法最好用於製備式I.1中R3 為H之化合物。因此，可採用如上述說明之製程，使用化合物IX為醛XII(相當於化合物IX，其中R3 為H)，其會與膦酸酯XVII反應。此方法說明於下列反應圖： This process is preferably used to prepare compounds of formula I.1 wherein R 3 is H. Thus, the procedure described above can be employed, using compound IX as the aldehyde XII (corresponding to compound IX wherein R 3 is H) which will react with the phosphonate XVII. This method is illustrated in the following reaction chart:

反應圖中，代號A1 、A2 、R1 、R2 、R4 、R5 、R6 、Ra 、Rb 、Rc 、Rd 、Re 與Rf 如上述定義。Ry 為C1 －C4 －烷基，例如：甲基、乙基、丙基、異丙基、正丁基或異丁基，芳基，例如：苯基，或芳基－C1 －C4 －烷基，例如：苯甲基。Ry 為C1 －C4 －烷基較佳，特定言之甲基或乙基。In the reaction scheme, the symbols A 1 , A 2 , R 1 , R 2 , R 4 , R 5 , R 6 , R a , R b , R c , R d , R e and R f are as defined above. R y is C 1 -C 4 -alkyl, for example: methyl, ethyl, propyl, isopropyl, n-butyl or isobutyl, aryl, for example phenyl, or aryl-C 1 - C 4 -alkyl, for example: benzyl. R y is preferably C 1 -C 4 -alkyl, specifically methyl or ethyl.

合適反應條件係先前技藝習知者，且說明於例如：J.Org.Chem.2001,66(11),3984－3997與Tetrahedron Lett.1987,28,4275，其揭示內容已以引用方式完全併入本文中。Suitable reaction conditions are known to those skilled in the art and are described, for example, in J. Org. Chem. 2001, 66 (11), 3984-3997 and Tetrahedron Lett. 1987, 28, 4275, the disclosure of which is incorporated herein by reference. Into this article.

因此合適鹼類為所有常用於威特－豪尼－艾蒙斯反應之鹼類，例如：鹼金屬氫化物，如：氫化鈉，與鹼金屬胺化物，如：二異丙基胺化鋰。然而，最好使用相當弱鹼類，如，例如：如上述非親核性鹼類，例如：脒類DBU與DBN或立體上受遮蔽之鹼金屬醇鹽，如：第三丁醇鉀。合適溶劑當然為非質子性，且係選自例如：鹵化烴類，如：二氯甲烷、氯仿與氯苯，及芳香烴類，如：苯與甲苯。Suitable bases are therefore all bases commonly used in the Witt-Hauni-Emmons reaction, such as alkali metal hydrides such as sodium hydride, and alkali metal amides such as lithium diisopropylamide. However, it is preferred to use relatively weak bases such as, for example, the above non-nucleophilic bases such as guanidines DBU and DBN or stereoscopically masked alkali metal alkoxides such as potassium t-butoxide. Suitable solvents are of course aprotic and are selected, for example, from halogenated hydrocarbons such as dichloromethane, chloroform and chlorobenzene, and aromatic hydrocarbons such as benzene and toluene.

原則上，威特－豪尼－艾蒙斯反應亦可用於製備式I中R3 不一定為氫但卻亦可為C1 －C6 －烷基、C3 －C6 －環烷基、C2 －C6 －烯基、C3 －C6 －環烯基、C2 －C6 －炔基、C3 －C6 －環炔基、苯基、苯基－(C1 －C6 )－烷基、雜環基、雜環基－(C1 －C6 )－烷基；苯基－[C1 －C6 －烷氧基羰基]－(C1 －C6 )－烷基或苯基雜環基－(C1 －C6 )－烷基，尤指C1 －C6 －烷基之化合物。此時，可改用酮IX.1(相當於式IX中R3 不為氫之化合物)替代醛XII 其中R3 為C1 －C6 －烷基、C3 －C6 －環烷基、C2 －C6 －烯基、C3 －C6 －環烯基、C2 －C6 －炔基、C3 －C6 －環炔基、苯基、苯基－(C1 －C6)－烷基、雜環基、雜環基－(C1 －C6 )－烷基；苯基－[C1 －C6－烷氧基羰基]－(C1 －C6 )－烷基或苯基雜環基－(C1 －C6 )－烷基，尤指C1 －C6 －烷基。In principle, the Witt-Hauni-Emmons reaction can also be used in the preparation of formula I wherein R 3 is not necessarily hydrogen but can also be C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 2 -C 6 -alkenyl, C 3 -C 6 -cycloalkenyl, C 2 -C 6 -alkynyl, C 3 -C 6 -cycloalkynyl, phenyl, phenyl-(C 1 -C 6 -alkyl, heterocyclic, heterocyclyl-(C 1 -C 6 )-alkyl; phenyl-[C 1 -C 6 -alkoxycarbonyl]-(C 1 -C 6 )-alkyl Or a phenylheterocyclyl-(C 1 -C 6 )-alkyl group, especially a C 1 -C 6 -alkyl compound. In this case, ketone IX.1 (corresponding to the compound of formula IX where R 3 is not hydrogen) can be used instead of aldehyde XII. Wherein R 3 is C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 2 -C 6 -alkenyl, C 3 -C 6 -cycloalkenyl, C 2 -C 6 -alkynyl , C 3 -C 6 -cycloalkynyl, phenyl, phenyl-(C 1 -C6)-alkyl, heterocyclic, heterocyclyl-(C 1 -C 6 )-alkyl; phenyl-[ C 1 -C 6 -alkoxycarbonyl]-(C 1 -C 6 )-alkyl or phenylheterocyclyl-(C 1 -C 6 )-alkyl, especially C 1 -C 6 -alkyl.

此時，亦可採用如上述式I.1哌化合物之製法。然而大多數例子中需要更強烈之反應條件，例如：更強之鹼類、更高之溫度、更長之反應時間，等等，以便優先進行如上述威特－豪尼－艾蒙斯反應製備化合物I.1。At this time, a pipe as in the above formula I.1 can also be used. The preparation method of the compound. However, in most cases, more intense reaction conditions are required, such as: stronger bases, higher temperatures, longer reaction times, etc., in order to preferentially prepare the Witt-Honey-Emmons reaction as described above. Compound I.1.

膦酸酯XVII可例如：由膦酸酯XVIII環化製得： Phosphonate XVII can be prepared, for example, by cyclization of phosphonate XVIII:

反應圖中，代號Ry 、A2 、R1 、R2 、R4 、R5 、R6 、Rd 、Re 與Rf 如上述定義。ORx 為利用氧附接之脫離基，其中Rx 為C1 －C6 －烷基較佳，如：甲基、乙基、丙基、異丙基、正丁基、異丁基、戊基或己基，或苯基－C1 －C6 －烷基，如：苯甲基。In the reaction scheme, the symbols R y , A 2 , R 1 , R 2 , R 4 , R 5 , R 6 , R d , R e and R f are as defined above. OR x is a leaving group attached by oxygen, wherein R x is preferably C 1 -C 6 -alkyl, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl Or a hexyl group, or a phenyl-C 1 -C 6 -alkyl group, such as a benzyl group.

該環化法係類似如上述化合物IV形成化合物II之環化法所說明反應進行。This cyclization process is carried out analogously to the reaction described by the cyclization method for the formation of compound II of the above compound IV.

膦酸酯XVIII製法可由先前製備之N－脫除保護基之膦酸酯XIX與N－受保護之胺基酸XX偶合後，脫除保護基： The phosphonate XVIII process can be carried out by coupling the previously prepared N-deprotection group phosphonate XIX with the N-protected amino acid XX to remove the protecting group:

反應圖中，代號Rx 、Ry 、A2 、R1 、R2 、R4 、R5 、R6 、Rd 、Re 與Rf 如上述定義。Cbz為苯甲基氧羰基保護基。除了Cbz與Boc，亦可改用其他胺基保護基替代。In the reaction scheme, the symbols R x , R y , A 2 , R 1 , R 2 , R 4 , R 5 , R 6 , R d , R e and R f are as defined above. Cbz is a benzyloxycarbonyl protecting group. In addition to Cbz and Boc, other amine protecting groups can be used instead.

Cbz保護基通常使用氫，於鈀/碳之存在下進行還原反應脫除。亦可採用其他常用於脫除Cbz基團之方法。若採用其他保護基時，通常依據適合脫除該基團之反應進行。The Cbz protecting group is usually removed using hydrogen in the presence of palladium on carbon. Other methods commonly used to remove the Cbz group can also be employed. If other protecting groups are employed, they are usually carried out in accordance with a reaction suitable for the removal of the group.

如上述反應可依據Tetrahedron 2004,60,961－965說明之方法進行。因此，步驟2中，與胺基酸XX之偶合法係類似由化合物VI與VII製備化合物V之方法進行。化合物XXI脫除保護基形成化合物XVIII之方法係類似化合物V脫除保護基形成化合物IV之方法進行。The above reaction can be carried out according to the method described in Tetrahedron 2004, 60, 961-965. Therefore, in the step 2, the method of preparing the compound V from the compounds VI and VII is carried out similarly to the coupling law of the amino acid XX. The method of removing the protecting group from the compound XXI to form the compound XVIII is carried out by a method similar to the removal of the protecting group from the compound V to form the compound IV.

膦酸酯類XIX為自商品取得或可依據Synthesis 1986,53－60說明之方法製備。The phosphonates XIX are either commercially available or can be prepared according to the methods described in Synthesis 1986, 53-60.

製法ESystem E

本發明進一步提供一種製備通式I哌化合物之方法，其包括於鹼之存在下，由式IX化合物 其中代號A1 、Ra 、Rb 與Rc 如上述定義，R3 為氫、C1 －C6 －烷基、C3 －C6 －環烷基、C2 －C6 －烯基、C3 －C6 －環烯基、C2 －C6 －炔基、C3 －C6 －環炔基、苯基、苯基－(C1 －C6 )－烷基、雜環基、雜環基－(C1 －C6 )－烷基、苯基－[C1 －C6 －烷氧基羰基]－(C1 －C6 )－烷基或苯基雜環基－(C1 －C6 )－烷基，與式XXI膦酸酯反應 其中代號A2 、R1 、R2 、R4 、R5 、R6 、Rd 、Re 與Rf 如上述定義，ORx 為利用氧附接之脫離基，其中Rx 為C1 －C6 －烷基，如：甲基、乙基、丙基、異丙基、正丁基、異丁基、戊基或己基較佳，或苯基－C1 －C6 －烷基，如：苯甲基，Ry 為C1 －C4 －烷基，例如：甲基、乙基、丙基、異丙基、正丁基或異丁基，芳基，例如：苯基，或芳基－C1 －C4 －烷基，例如：苯甲基，及SG為胺基保護基，例如：Boc，產生式XXII化合物 脫除胺基保護基，產生式XXIII化合物 並由式XXIII化合物環化，形成式I化合物。The invention further provides a preparation of the formula I a method of a compound comprising a compound of formula IX in the presence of a base Wherein the codes A 1 , R a , R b and R c are as defined above, and R 3 is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 2 -C 6 -alkenyl, C 3 -C 6 -cycloalkenyl, C 2 -C 6 -alkynyl, C 3 -C 6 -cycloalkynyl, phenyl, phenyl-(C 1 -C 6 )-alkyl, heterocyclic, Heterocyclyl-(C 1 -C 6 )-alkyl, phenyl-[C 1 -C 6 -alkoxycarbonyl]-(C 1 -C 6 )-alkyl or phenylheterocyclyl-(C 1 -C 6 )-alkyl group, reacted with a phosphonate of the formula XXI Wherein the codes A 2 , R 1 , R 2 , R 4 , R 5 , R 6 , R d , R e and R f are as defined above, and OR x is a leaving group attached by oxygen, wherein R x is C 1 - C 6 -alkyl, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl or hexyl, or phenyl-C 1 -C 6 -alkyl, such as : benzyl, R y is C 1 -C 4 -alkyl, for example: methyl, ethyl, propyl, isopropyl, n-butyl or isobutyl, aryl, for example: phenyl, or aryl a base-C 1 -C 4 -alkyl group, for example: benzyl, and SG is an amine protecting group, for example: Boc, to give a compound of formula XXII Removal of the amine protecting group to yield a compound of formula XXIII And cyclized from a compound of formula XXIII to form a compound of formula I.

根據本發明製法之第一個步驟亦稱為威特－豪尼－艾蒙斯反應。The first step of the process according to the invention is also known as the Witt-Hauni-Emmons reaction.

Ry 為C1 －C4 －烷基較佳，特定言之甲基或乙基。R y is preferably C 1 -C 4 -alkyl, specifically methyl or ethyl.

最好採用根據本發明製法製備式I.1中R3 為H之化合物。因此可採用如上述製法，其中採用醛XII(相當於式IX中R3 為H之化合物)進行威特－豪尼－艾蒙斯反應。使用開鏈膦酸酯XXI.1，後者轉化成式XXII.1烯烴，當脫除保護基後，即環化成哌I.1，如下列反應圖所示： It is preferred to prepare a compound of formula I.1 wherein R 3 is H according to the process of the invention. Thus, a Witt-Doney-Emmons reaction using the aldehyde XII (corresponding to a compound of the formula IX wherein R 3 is H) can be employed. Using the open-chain phosphonate XXI.1, the latter is converted to the olefin of the formula XXII.1, and after removal of the protecting group, it is cyclized to the piperidine I.1, as shown in the following reaction diagram:

式I.1、XII、XXI、XXII.1與XXIII.1中，代號A1 、A2 、R1 －R6 、Ra 、Rb 、Rc 、Rd 、Re 與Rf 如式I之定義。ORx 為利用氧附接之脫離基，其中Rx 為C1 －C6 －烷基較佳，如：甲基、乙基、丙基、異丙基、正丁基、異丁基、戊基或己基，或苯基－C1 －C6 －烷基，如：苯甲基。Ry 為C1 －C4 －烷基，例如：甲基、乙基、丙基、異丙基、正丁基或異丁基，芳基，例如：苯基，或芳基－C1 －C4 －烷基，例如：苯甲基。Ry 為C1 －C4 －烷基較佳，特定言之甲基或乙基。SG為合適胺基保護基，特定言之Boc。In the formulae I.1, XII, XXI, XXII.1 and XXIII.1, the codes A 1 , A 2 , R 1 - R 6 , R a , R b , R c , R d , R e and R f are as defined The definition of I. OR x is a leaving group attached by oxygen, wherein R x is preferably C 1 -C 6 -alkyl, such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, pentyl Or a hexyl group, or a phenyl-C 1 -C 6 -alkyl group, such as a benzyl group. R y is C 1 -C 4 -alkyl, for example: methyl, ethyl, propyl, isopropyl, n-butyl or isobutyl, aryl, for example: phenyl, or aryl-C 1 - C 4 -alkyl, for example: benzyl. R y is preferably C 1 -C 4 -alkyl, specifically methyl or ethyl. SG is a suitable amine protecting group, specifically Boc.

膦酸酯XXI與醛XII之反應可類似如上述膦酸酯XVII與醛XII之反應進行。該反應亦可類似Synthesis 1992,487－490,Synthesis 1992,482－486與Synthesis 1984,53－60說明之反應進行，其揭示內容已以引用方式完全併入本文中。The reaction of the phosphonate XXI with the aldehyde XII can be carried out analogously to the reaction of the above phosphonate XVII with the aldehyde XII. This reaction can also be carried out analogously to the reactions described in Synthesis 1992, 487-490, Synthesis 1992, 482-486 and Synthesis 1984, 53-60, the disclosure of which is hereby incorporated by reference in its entirety.

保護基通常依文獻中已知方法脫除。若例如：SG為Boc時，保護基可如上述化合物V說明之方法脫除，例如：由化合物XXII.1與酸反應。該脫除保護基反應亦可類似Tetrahedron 2004,60,961－965說明之方法進行，其揭示內容已以引用方式併入本文中。The protecting groups are usually removed by methods known in the literature. For example, when SG is Boc, the protecting group can be removed by the method described in the above compound V, for example, by reacting the compound XXII.1 with an acid. The deprotection group reaction can also be carried out analogously to the method described in Tetrahedron 2004, 60, 961-965, the disclosure of which is incorporated herein by reference.

二肽XXIII.1形成哌I.1之環化法可類似化合物IV形成化合物II之轉化法進行。然而，此時僅適合在酸之存在下進行環化法，因為其中含有雙鍵。此時，適合採用化合物IV之環化法，且同樣適合採用其較佳酸類與溶劑。酸性環化法亦可依據Tetrahedron 2004,60,961－965說明之製法進行，其揭示內容已以引用方式併入本文中。Dipeptide XXIII.1 forms a pipe The cyclization of I.1 can be carried out analogously to the conversion of Compound IV to Form II. However, at this time, it is only suitable to carry out the cyclization method in the presence of an acid because it contains a double bond. In this case, the cyclization method of the compound IV is suitably employed, and it is also suitable to use the preferred acid and solvent. Acid cyclization can also be carried out in accordance with the process described in Tetrahedron 2004, 60, 961-965, the disclosure of which is incorporated herein by reference.

除了使用保護N，例如：Boc－保護之化合物XXI.1外，亦可使用化相應之脫除保護基之化合物進行威特－豪尼－艾蒙斯反應，以直接形成化合物XXIII.1。保護基通常依文獻中已知方法脫除。若例如：SG為Boc時，可依上述化合物V之說明，脫除化合物XXI之Boc保護基，例如：由化合物XXI與酸反應。脫除保護基反應亦可類似Tetrahedron 2004,60,961－965說明之方法進行，其揭示內容已以引用方式併入本文中。In addition to the use of a protecting N, for example a Boc-protected compound XXI.1, a Witt-Honey-Emmons reaction can be carried out using a corresponding deprotecting compound to form a compound XXIII.1 directly. The protecting groups are usually removed by methods known in the literature. For example, when SG is Boc, the Boc protecting group of compound XXI can be removed according to the description of compound V above, for example, by reacting compound XXI with an acid. The removal of the protecting group reaction can also be carried out analogously to the method described in Tetrahedron 2004, 60, 961-965, the disclosure of which is incorporated herein by reference.

原則上，依據本發明製法亦可用於製備式I中R3 不一定為氫，但卻可為C1 －C6 －烷基、C3 －C6 －環烷基、C2 －C6 －烯基、C3 －C6 －環烯基、C2 －C6 －炔基、C3 －C6 －環炔基、苯基、苯基－(C1 －C6 )－烷基、雜環基、雜環基－(C1 －C6 )－烷基；苯基－[C1 －C6 －烷氧基羰基]－(C1 －C6 )－烷基或苯基雜環基－(C1 －C6 )－烷基，尤指C1 －C6 －烷基之化合物。此時，可改用酮IX.1替代醛XII。In principle, the process according to the invention can also be used in the preparation of formula I wherein R 3 is not necessarily hydrogen, but can be C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 2 -C 6 - Alkenyl, C 3 -C 6 -cycloalkenyl, C 2 -C 6 -alkynyl, C 3 -C 6 -cycloalkynyl, phenyl, phenyl-(C 1 -C 6 )-alkyl, hetero Cyclo, heterocyclyl-(C 1 -C 6 )-alkyl; phenyl-[C 1 -C 6 -alkoxycarbonyl]-(C 1 -C 6 )-alkyl or phenyl heterocyclyl -(C 1 -C 6 )-alkyl, especially a C 1 -C 6 -alkyl compound. At this time, ketone IX.1 can be used instead of aldehyde XII.

其中R3 為C1 －C6 －烷基、C3 －C6 －環烷基、C2 －C6 －烯基、C3 －C6 －環烯基、C2 －C6 －炔基、C3 －C6 －環炔基、苯基、苯基－(C1 －C6 )－烷基、雜環基、雜環基－(C1 －C6 )－烷基；苯基－[C1 －C6 －烷氧基羰基]－(C1 －C6 )－烷基或苯基雜環基－(C1 －C6 )－烷基，尤指C1 －C6 －烷基。 Wherein R 3 is C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 2 -C 6 -alkenyl, C 3 -C 6 -cycloalkenyl, C 2 -C 6 -alkynyl , C 3 -C 6 -cycloalkynyl, phenyl, phenyl-(C 1 -C 6 )-alkyl, heterocyclic, heterocyclyl-(C 1 -C 6 )-alkyl; phenyl- [C 1 -C 6 -alkoxycarbonyl]-(C 1 -C 6 )-alkyl or phenylheterocyclyl-(C 1 -C 6 )-alkyl, especially C 1 -C 6 -alkane base.

此時，亦可採用如上述式I.1哌化合物之製法。然而大多數例子中需要更強烈之反應條件，例如：更強之鹼類、更高之溫度、更長之反應時間，等等，以便採用經由膦酸酯XXI製備化合物I之方法來製備化合物I.1。At this time, a pipe as in the above formula I.1 can also be used. The preparation method of the compound. However, in most cases, more intense reaction conditions are required, such as: stronger bases, higher temperatures, longer reaction times, etc., in order to prepare compound I by the method of preparing compound I via phosphonate XXI. .1.

製法FSystem F

式I中R1 ≠氫之化合物製法亦可由式I中R1 為氫之哌化合物，與包含不為氫之基團R1 之烷化劑或醯化劑反應。此等反應可類似文獻中已知方法進行，例如：依據I.O.Donkor等人之Bioorg.Med.Chem.Lett.11(19)(2001),2647－2649、B.B.Snider等人之Tetrahedron 57(16)(2001),3301－3307,I.Yasuhiro等人之J.Am.Chem.Soc.124(47)(2002),14017－14019或M.Falorni等人之Europ.J.Org.Chem.(8)(2000),1669－1675說明之方法。Formula I wherein R 1 ≠ hydrogen the compound may also be prepared by the method of formula I wherein R 1 is hydrogen of piperazine a compound which is reacted with an alkylating or deuterating agent comprising a group R 1 which is not hydrogen. Such reactions can be carried out analogously to methods known in the literature, for example, according to Ionkor et al., Bioorg. Med. Chem. Lett. 11 (19) (2001), 2647-2649, BBSnider et al., Tetrahedron 57 (16) (2001). ), 3301-3307, J. Am. Chem. Soc. 124 (47) (2002), 14017-14019 by M. Falorni et al. 2000), the method described in 1669-1675.

因此，由I中R1 ＝氫之哌化合物與合適烷化劑(下文中稱為化合物X1 －R1 )或醯化劑(下文中稱為化合物X2 －R1 )反應，產生式I哌化合物，其中R1 ≠氫。Therefore, from I in the R 1 = hydrogen pipe The compound is reacted with a suitable alkylating agent (hereinafter referred to as compound X 1 -R 1 ) or a oximation agent (hereinafter referred to as compound X 2 -R 1 ) to give a pipe of formula I a compound wherein R 1 is hydrogen.

烷化劑X1 －R1 中，X1 可為鹵素或O－SO2 －Rm ，其中Rm 為C1 －C4 －烷基或芳基，其可視需要經鹵素、C1 －C4 －烷基或鹵－C1 －C4 －烷基取代。醯化劑X2 －R1 中，X2 可為鹵素，特定言之C1 。此時，R1 ≠氫，且如上述定義，特定言之C1 －C6 －烷基、C3 －C6 －環烷基、C3 －C6 －烯基、C3 －C6 －環烯基、C3 －C6 －炔基、C3 －C6 －環炔基、苯基－(C1 －C6 )－烷基、雜環基、雜環基－(C1 －C6 )－烷基；苯基－[C1 －C6 －烷氧基羰基]－(C1 －C6 )－烷基或苯基雜環基－(C1 －C6 )－烷基；或COR21 或SO2 R25 ，其中R1 之如上述脂系、環狀或芳香系部份基團可部份或完全鹵化與/或可帶有1至3個下列基團：氰基、羥基、C1 －C4 －烷基、C1 －C4 －鹵烷基、C3 －C6 －環烷基、C1 －C4 －烷氧基、C1 －C4 －烷基硫、[二－(C1 －C4 )－烷基]胺基、C1 －C4 －烷基羰基、羥基羰基、C1 －C4 －烷氧基羰基、胺基羰基、C1 －C4 －烷基胺基羰基、[二－(C1 －C4 )－烷基]胺基羰基或C1 －C4 －烷基羰基氧。In the alkylating agent X 1 -R 1 , X 1 may be halogen or O-SO 2 -R m , wherein R m is C 1 -C 4 -alkyl or aryl, which may optionally be halogen, C 1 -C 4 -alkyl or halo-C 1 -C 4 -alkyl substituted. In the oxime agent X 2 -R 1 , X 2 may be a halogen, specifically C 1 . In this case, R 1 is hydrogen, and as defined above, specifically C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 -alkenyl, C 3 -C 6 - Cycloalkenyl, C 3 -C 6 -alkynyl, C 3 -C 6 -cycloalkynyl, phenyl-(C 1 -C 6 )-alkyl, heterocyclyl, heterocyclyl-(C 1 -C 6 )-alkyl; phenyl-[C 1 -C 6 -alkoxycarbonyl]-(C 1 -C 6 )-alkyl or phenylheterocyclyl-(C 1 -C 6 )-alkyl; Or COR 21 or SO 2 R 25 , wherein the above aliphatic, cyclic or aromatic moiety of R 1 may be partially or completely halogenated and/or may have from 1 to 3 of the following groups: cyano, Hydroxy, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 3 -C 6 -cycloalkyl, C 1 -C 4 -alkoxy, C 1 -C 4 -alkylthio , [di-(C 1 -C 4 )-alkyl]amino, C 1 -C 4 -alkylcarbonyl, hydroxycarbonyl, C 1 -C 4 -alkoxycarbonyl, aminocarbonyl, C 1 -C 4 -alkylaminocarbonyl, [di-(C 1 -C 4 )-alkyl]aminocarbonyl or C 1 -C 4 -alkylcarbonyloxy.

該反應通常在－78℃至該反應混合物之沸點之溫度範圍進行，較佳為－50℃至65℃，特別佳為－30℃至65℃。通常，該反應係在溶劑中進行，較佳為在惰性有機溶劑中進行。The reaction is usually carried out at a temperature ranging from -78 ° C to the boiling point of the reaction mixture, preferably from -50 ° C to 65 ° C, particularly preferably from -30 ° C to 65 ° C. Usually, the reaction is carried out in a solvent, preferably in an inert organic solvent.

合適溶劑為製法B(二肽IV形成哌II之環化法)所述及之溶劑，特別指甲苯、二氯甲烷、四氫呋喃或二甲基甲醯胺或其混合物。A suitable solvent is Process B (dipeptide IV forms a pipe The solvent referred to in the cyclization method of II is specifically referred to as toluene, dichloromethane, tetrahydrofuran or dimethylformamide or a mixture thereof.

本發明較佳具體實施例中，該反應係在四氫呋喃中進行。In a preferred embodiment of the invention, the reaction is carried out in tetrahydrofuran.

較佳具體實施例中，由化合物I，其中R1 ＝H，與烷化劑或醯化劑，於鹼之存在下反應。合適鹼類為製法B(二肽IV形成哌II之環化法)所述及之化合物。該鹼類通常使用等莫耳量。亦可使用過量或甚至作為溶劑。較佳具體實施例中，鹼之添加量為等莫耳量或實質上等莫耳量。亦較佳之具體實施例中，所使用之鹼為氫化鈉。In a preferred embodiment, compound I, wherein R 1 = H, is reacted with an alkylating or deuterating agent in the presence of a base. The suitable base is Process B (dipeptide IV forms a pipe The compound described in the cyclization method of II). The base is usually used in an equivalent molar amount. Excess or even as a solvent can also be used. In a preferred embodiment, the amount of base added is an equivalent molar amount or substantially equal to the molar amount. In a preferred embodiment, the base used is sodium hydride.

操作法通常係類似製法B(二肽IV形成哌II之環化法)說明之方法進行。The method of operation is usually similar to the preparation method B (dipeptide IV formation of piperidine The method of cyclization of II) is carried out.

或者，基團NR1 中R1 為H之烷化法或醯化法亦可在前體中進行。因此，例如：式II、IV、V、XIII、XIV、XVI、XXII或XXIII中R1 為H之化合物可如上述說明進行N－烷化或N－醯化反應。Alternatively, the alkylation or deuteration in which R 1 is H in the group NR 1 can also be carried out in the precursor. Thus, for example, a compound of formula II, IV, V, XIII, XIV, XVI, XXII or XXIII wherein R 1 is H can be subjected to an N-alkylation or N-deuteration reaction as described above.

製法GSystem G

類似上述說明之方法，其中R2 為氫之化合物I或其前體可與烷化劑R2 －X1 或醯化劑R2 －X2 反應，產生其中R2 ≠氫之式I或其前體。該反應條件相當於上述條件。A process analogous to that described above, wherein the compound I wherein R 2 is hydrogen or a precursor thereof is reacted with an alkylating agent R 2 -X 1 or a oximation agent R 2 -X 2 to give formula I wherein R 2 is hydrogen or Precursor. This reaction condition corresponds to the above conditions.

製法HMethod H

此外，式I化合物可於基團A1 上修飾。因此其可例如：依據下列反應圖說明之製法，轉化取代基Ra 製成，例如：類似J.Tsuji,Top.Organomet.Chem.(14)(2005),332 pp.或J.Tsuji,Organic Synthesis with Palladium化合物(1980),207 pp.說明之方法進行。Furthermore, the compounds of formula I can be modified on the group A 1 . Thus, for example, it can be prepared by converting the substituent R a according to the following scheme of the reaction scheme, for example: similar to J. Tsuji, Top. Organomet. Chem. (14) (2005), 332 pp. or J. Tsuji, Organic Synthesis with Palladium Compound (1980), 207 pp.

因此，其中改用合適脫離基L替代取代基Ra 之式I哌化合物可與包含基團Ra 之偶合劑(化合物Ra －X3 )反應，轉化成另一種式I哌衍生物。Therefore, in which a suitable cleavage group L is used instead of the substituent R a The compound can be reacted with a coupling agent containing the group R a (compound R a -X 3 ) to be converted into another formula I derivative.

該反應通常在觸媒之存在下進行，較佳為在過渡金屬觸媒之存在下進行。通常，該反應在鹼之存在下進行。The reaction is usually carried out in the presence of a catalyst, preferably in the presence of a transition metal catalyst. Usually, the reaction is carried out in the presence of a base.

此反應順序以取代基Ra 為例說明，且當然依類似方式用於轉化取代基Rb 與Rc 。This reaction sequence is illustrated by the substituent R a and is of course used in a similar manner to convert the substituents R b and R c .

合適脫離基L為例如：鹵素或S(O)n Rk ，其中n＝0、1、2，Rk 為C1 －C6 －烷基、鹵－(C1 －C6 )－烷基或可視需要鹵化或C1 －C4 －烷基－取代之芳基。Suitable exfoliating groups L are, for example, halogen or S(O) n R k , wherein n=0, 1, 2, R k is C 1 -C 6 -alkyl, halo-(C 1 -C 6 )-alkyl Alternatively, a halogenated or C 1 -C 4 -alkyl-substituted aryl group may be used.

合適偶合試劑X3 －Ra 特定言之為彼等其中若Ra 為C1 －C6 －烷基、C2 －C6 －烯基、芳基或雜芳基時，X3 代表下列基團之化合物：－Zn－R1 ，其中R1 為鹵素、C1 －C6 －烷基、C2 －C6 －烯基、芳基或雜芳基；－B(ORm )2 ，其中Rm 為H或C1 －C6 －烷基，其中兩個烷基取代基可共同形成C2 －C4 －伸烷基鏈；或－SnRn 3 ，其中Rn 為C1 －C6 －烷基或芳基。Suitable coupling reagents X 3 -R a are specifically those in which, if R a is C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, aryl or heteroaryl, X 3 represents the following group a compound of the group: -Zn-R 1 wherein R 1 is halogen, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, aryl or heteroaryl; -B(OR m ) 2 , wherein R m is H or C 1 -C 6 -alkyl, wherein two alkyl substituents may together form a C 2 -C 4 -alkyl chain; or -SnR n 3 , wherein R n is C 1 -C 6 - alkyl or aryl.

若Ra 為C2 －C6 －炔基時，X3 亦不可為氫。If R a is a C 2 -C 6 -alkynyl group, X 3 may not be hydrogen.

式I中Ra 為CN之化合物製法可由化合物Ia(其中L為溴或碘)與氰化酮類似已知方法反應(參見例如："有機化學(Organikum)"，第21版，2001,Wiley,p.404與其中摘錄之文獻)。The preparation of a compound of formula I wherein R a is CN can be carried out by a known method analogous to cyanide by the use of compound Ia (wherein L is bromine or iodine) (see for example: "Organicum", 21st edition, 2001, Wiley, P.404 and the excerpts from it).

此時，依據較佳具體實施例，式I中之L或Ra 係附接在A1 與A1 之碳原子之附接點之鄰位。In this case, according to preferred specific embodiment of Formula I, L, or R a line attached to the carbon ortho to the point of attachment of A 1 and A 1 atoms.

此反應通常在－78℃至該反應混合物之沸點之範圍內進行，較佳為－30℃至65℃，特別佳為30℃至65℃之溫度間。通常，該反應在惰性有機溶劑中，於鹼之存在下進行。The reaction is usually carried out at a temperature ranging from -78 ° C to the boiling point of the reaction mixture, preferably from -30 ° C to 65 ° C, particularly preferably from 30 ° C to 65 ° C. Usually, the reaction is carried out in an inert organic solvent in the presence of a base.

合適溶劑為製法B(二肽IV形成哌II之環化法)所述及之化合物。根據本發明製法之一項具體實施例中，係使用四氫呋喃與觸媒量之水；另一項具體實施例中，僅使用四氫呋喃。A suitable solvent is Process B (dipeptide IV forms a pipe The compound described in the cyclization method of II). In a specific embodiment of the process of the present invention, tetrahydrofuran is used in combination with water in a catalytic amount; in another embodiment, only tetrahydrofuran is used.

合適鹼類為製法B(二肽IV形成哌II之環化法)所述及之化合物。The suitable base is Process B (dipeptide IV forms a pipe The compound described in the cyclization method of II).

鹼類之用量通常為等莫耳量。亦可使用過量或甚至作為溶劑。The amount of base used is usually equal to the molar amount. Excess or even as a solvent can also be used.

根據本發明較佳具體實施例中，鹼之添加量為等莫耳量。亦較佳之具體實施例中，所使用之鹼為三乙基胺或碳酸銫，特別佳為碳酸銫。According to a preferred embodiment of the invention, the amount of base added is an equivalent molar amount. In a preferred embodiment, the base used is triethylamine or cesium carbonate, particularly preferably cesium carbonate.

適合根據本發明製法之觸媒原則上為過渡金屬化合物Ni、Fe、Pd或Cu。可能使用有機或無機化合物。可述及之實例為Pd(PPh3 )2 Cl2 、Pd(OAc)2 、PdCl2 或Na2 PdCl4 。其中Ph為苯基。The catalyst suitable for the process according to the invention is in principle a transition metal compound Ni, Fe, Pd or Cu. It is possible to use organic or inorganic compounds. Examples which may be mentioned are Pd(PPh 3 ) 2 Cl 2 , Pd(OAc) 2 , PdCl 2 or Na 2 PdCl 4 . Wherein Ph is a phenyl group.

不同之觸媒可分開使用或形成混合物使用。本發明較佳具體實施例中，使用Pd(PPh3 )2 Cl2 。Different catalysts can be used separately or as a mixture. In a preferred embodiment of the invention, Pd(PPh 3 ) 2 Cl 2 is used .

該操作法係類似製法B(二肽IV形成哌II之環化法)說明之製程進行。This method of operation is similar to Process B (dipeptide IV formation of piperidine) The cyclization method of II) describes the process.

或者，基團A1 之轉化法亦可使用化合物Ia之前體進行。例如：由化合物II、IV、V、VII、VIII、IX、XI與XII(其中改由基團L替代基團Ra 附接A1 )如上述進行反應。Alternatively, the conversion of the group A 1 can also be carried out using the precursor of the compound Ia. For example: a compound II, IV, V, VII, VIII, IX, XI and XII (wherein the group L by the grafting alternative radicals R a attached to A 1) is reacted as described above.

製法ISystem I

式I中一個Ra 、Rb 或Rc 基團為COOH之哌化合物亦可由式I中Ra 、Rb 或Rc 為COORz ，其中Rz 為烷基，例如：CH3 之哌化合物經水解酯基後製備。該水解反應可例如：與(H3 C)3 SnOH反應，例如：依據K.C.Nicolaou等人之Angew.Chem.Int.Ed.Engl.(44)(2005),1378說明之方法進行。依此方式所得羧酸可依標準有機合成法轉化，若適當時，在轉化成醯基氯後，與胺HNRu Rv 或醇HORw 反應，產生相應酯或醯胺(參見例如：Organikum、Autorenkollektiv,Leipzig 1993,19版，pp.424,429)。此反應順序於下文中採用取代基Ra 為例說明，但其中當然亦可能依類似方式使用此順序，轉化取代基Rb 與Rc 。A group of R a , R b or R c in formula I is a COOH The compound may also be from the formula I wherein R a , R b or R c is COOR z , wherein R z is alkyl, for example: CH 3 The compound is prepared after hydrolysis of the ester group. The hydrolysis reaction can be carried out, for example, by reaction with (H 3 C) 3 SnOH, for example, according to the method described by KCNicolaou et al., Angew. Chem. Int. Ed. Engl. (44) (2005), 1378. The carboxylic acid obtained in this manner can be converted by standard organic synthesis, if appropriate, after conversion to mercapto chloride, with the amine HNR u R v or the alcohol HOR w to give the corresponding ester or guanamine (see for example: Organikum, Autorenkollektiv, Leipzig 1993, 19th edition, pp. 424, 429). This reaction sequence is exemplified below using the substituent R a , but it is of course also possible to use this sequence in a similar manner to convert the substituents R b and R c .

此反應圖中，代號A1 、A2 、R1 －R6 、Rb 、Rc 、Rd 、Re 與Rf 如上述定義。Ru 與Rv 分別獨立為氫、C1 －C6 －烷基、C2 －C6 －烯基、C2 －C6 －炔基、C1 －C6 －烷氧基、C1 －C6 －烷基磺醯基、C1 －C6 －烷基胺基磺醯基、[二－(C1 －C6 )－烷基胺基]磺醯基或可視需要經取代之苯基。Rw 為C1 －C6 －烷基、C3 －C6 －烯基或C3 －C6 －炔基。Rz 為C1 －C6 －烷基、C3 －C6 －烯基、C3 －C6 －炔基、苯甲基，特定言之C1 －C4 －烷基。In the reaction scheme, the symbols A 1 , A 2 , R 1 - R 6 , R b , R c , R d , R e and R f are as defined above. R u and R v are each independently hydrogen, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 1 -C 6 -alkoxy, C 1 - C 6 -alkylsulfonyl, C 1 -C 6 -alkylaminosulfonyl, [di-(C 1 -C 6 )-alkylamino]sulfonyl or phenyl optionally substituted . R w is C 1 -C 6 -alkyl, C 3 -C 6 -alkenyl or C 3 -C 6 -alkynyl. R z is C 1 -C 6 -alkyl, C 3 -C 6 -alkenyl, C 3 -C 6 -alkynyl, benzyl, in particular C 1 -C 4 -alkyl.

第一個步驟中，由哌化合物I{Ra ＝COORz }之酯基水解。該水解反應可例如：與(H3 C)3 SnOH反應，產生I之游離酸{Ra ＝COOH}。轉化成游離酸之方法通常採用過量(H3 C)3 SnOH進行。通常，該反應在惰性有機溶劑中進行。合適溶劑特定言之包括二氯乙烷。通常，該反應在加溫下進行，例如：約80℃下。The first step, by the pipe The ester group of compound I{R a =COOR z } is hydrolyzed. The hydrolysis reaction can be, for example, reacted with (H 3 C) 3 SnOH to give a free acid of R {R a =COOH}. The method of conversion to the free acid is usually carried out using an excess of (H 3 C) 3 SnOH. Usually, the reaction is carried out in an inert organic solvent. Suitable solvents include, in particular, dichloroethane. Usually, the reaction is carried out under heating, for example, at about 80 °C.

第二個步驟中，酸I{Ra ＝COOH}轉化成其醯基氯(Ra ＝COCl)。該形成醯基氯之轉化法通常在10℃至50℃之溫度間進行，較佳為於室溫下進行，例如：25℃。通常，該反應在惰性有機溶劑中進行。合適溶劑特定言之包括二氯甲烷。較佳具體實施例中，該反應在二氯甲烷與觸媒量之二甲基甲醯胺中進行。氯化反應適合使用大量試劑，例如：草醯氯或亞硫醯氯。較佳為使用實質上等莫耳量之氯化劑，特定言之草醯氯。In the second step, the acid I{R a =COOH} is converted to its mercapto chloride (R a =COCl). The conversion method for forming mercapto chloride is usually carried out at a temperature of from 10 ° C to 50 ° C, preferably at room temperature, for example, 25 ° C. Usually, the reaction is carried out in an inert organic solvent. Suitable solvents include, in particular, dichloromethane. In a preferred embodiment, the reaction is carried out in dichloromethane and a catalytic amount of dimethylformamide. The chlorination reaction is suitable for use with a large number of reagents such as grass chloroform or sulfoxide. It is preferred to use a chlorinating agent which is substantially equal to the molar amount, in particular, grassy chlorine.

隨後與胺NHRu Rv 之反應通常在添加過量該胺下進行。該反應可在0℃至40℃之溫度範圍內進行，較佳為於室溫下進行，例如：25℃。Subsequent reaction with the amine NHR u R v is usually carried out with the addition of an excess of the amine. The reaction can be carried out at a temperature ranging from 0 ° C to 40 ° C, preferably at room temperature, for example, 25 ° C.

隨後與醇HORw 之反應通常在添加指定醇與三乙基胺二者下進行。Subsequent reaction with the alcohol HOR w is usually carried out with the addition of the specified alcohol and triethylamine.

該反應可在0℃至40℃之溫度範圍內進行，較佳為於室溫下，例如：25℃。The reaction can be carried out at a temperature ranging from 0 ° C to 40 ° C, preferably at room temperature, for example, 25 ° C.

該操作法係類似製法B(二肽IV形成哌II之環化法)說明之方法進行。This method of operation is similar to Process B (dipeptide IV formation of piperidine) The method of cyclization of II) is carried out.

化合物I與其農業上適用之鹽適合呈異構物混合物及純異構物兩種型式作為除草劑使用。其本身即合適或可適當調配成組合物。包含化合物I或Ia之除草組合物可極有效率地控制非作物區之植物生長，尤其在高施用率下。其可對抗作物(如：小麥、稻、玉米、大豆與棉花)中之闊葉雜草與草本雜草，且不會顯著傷害作物植株。此效果主要出現在低施用率下。Compound I and its agriculturally suitable salts are suitable for use as herbicides in the form of isomer mixtures and pure isomers. It is suitable per se or can be suitably formulated into a composition. Herbicidal compositions comprising Compound I or Ia are extremely efficient in controlling plant growth in non-crop areas, especially at high application rates. It fights broadleaf weeds and herbaceous weeds in crops such as wheat, rice, corn, soybeans and cotton without significantly harming crop plants. This effect mainly occurs at low application rates.

依所需施用法而定，化合物I或Ia或含其之除草組合物亦可用於許多種其他作物植物，消除不要之植物。合適作物實例如下：蔥(Allium cepa)、鳳梨(Ananas comosus)、落花生(Arachis hypogaea)、蘆筍(Asparagus officinalis)、燕麥(Avena sativa)、甜菜(Beta vulgaris spec.altissima、Beta vulgaris spec.rapa)、蕓苔(Brassica napus var.napus、Brassica napus var.napobrassica、Brassica rapa var.silvestris)、芥藍(Brassica oleracea)、黑芥菜(Brassica nigra)、山茶(Camellia sinensis)、紅花(Carthamus tinctorius)、山核桃(Carya illinoinensis)、檸檬(Citrus limon)、柑桔(Citrus sinensis)、咖啡(Coffea arabica、Coffea canephora、Coffea liberica)、甜瓜(Cucumis sativus)、狗牙根(Cynodon dactylon)、胡蘿蔔(Daucus carota)、油椰子(Elaeis guineensis)、蛇莓(Fragaria Vesca)、大豆(Glycine max)、陸地棉(Gossypium hirsutum)、棉花(Gossypium arboreum、Gossypium herbaceum、Gossypium vitifolium)、向日葵(Helianthus annuus)、巴西橡膠樹(Hevea brasiliensis)、大麥(Hordeum vulgare)、啤酒花(Humulus lupulus)、甘薯(Ipomoea batatas)、胡桃(Juglans regia)、靈視豆(Lens culinaris)、亞麻(Linum usitatissimum)、番茄(Lycopersicon lycopersicum)、蘋果(Malus spec.)、白附子(Manihot esculenta)、苜蓿(Medicago sativa)、芭蕉(Musa spec.)、菸草(Nicotiana tabacum(N.rustica))、歐洲橄欖(Olea europaea)、稻(Oryza sativa)、利馬豆(Phaseolus lunatus)、菜豆(Phaseolus vulgaris)、雲杉(Picea abies)、松(Pinus spec.)、開心果(Pistacia vera)、豌豆(Pisum sativum)、梅(Prunus avium)、櫻(Prunus persica)、梨(Pyrus communis)、山杏(Prunus armeniaca)、酸櫻桃(Prunus cerasus)、扁桃(Prunus dulcis)與洋李(Prunus domestica)、醋栗(Ribes sylvestre)、蓖麻(Ricinus communis)、甘蔗(Saccharum officinarum)、黑麥(Secale cereale)、白芥(Sinapis alba)、茄(Solanum tuberosum)、高粱(Sorghum bicolor(s.vulgare))、可可樹(Theobroma cacao)、三葉草(Trifolium pratense)、黑小麥(Triticale)、普通小麥(Triticum aestivum)、硬粒小麥(Triticum durum)、蠺豆(vicia faba)、葡萄(vitis vinifera)與玉米(Zea mays)。Depending on the desired method of application, the compound I or Ia or the herbicidal compositions therewith can also be used in a wide variety of other crop plants to eliminate unwanted plants. Examples of suitable crops are as follows: Allium cepa, Ananas comosus, Arachis hypogaea, Asparagus officinalis, Avena sativa, Beet (Beta vulgaris spec.altissima, Beta vulgaris spec.rapa), Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Brassica oleracea, Brassica nigra, Camellia sinensis, Carthamus tinctorius, pecan (Carya illinoinensis), Citrus limon, Citrus sinensis, Coffee (Coffea arabica, Coffea canephora, Coffea liberica), Cucumis sativus, Cynodon dactylon, Carrot (Daucus carota), oil Coconut (Elaeis guineensis), Fragaria Vesca, Glycine max, Gossypium hirsutum, Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium, Helianthus annuus, Hevea brasiliensis , barley (Hordeum vulgare), hops (Humulus lupulus), sweet potato (Ipomoea batatas), Hu Juglans regia, Lens culinaris, Linum usitatissimum, Lycopersicon lycopersicum, Malus spec., Manihot esculenta, Medicago sativa, Musa spec .), Tobacco (Nicotiana tabacum (N.rustica)), European olive (Olea europaea), Rice (Oryza sativa), Lima bean (Phaseolus lunatus), Kidney bean (Phaseolus vulgaris), Spruce (Picea abies), pine ( Pinus spec.), Pistacia vera, Pisum sativum, Prunus avium, Prunus persica, Pyrus communis, Prunus armeniaca, Prunus cerasus, Prunus dulcis and Prunus domestica, Ribes sylvestre, Ricinus communis, Saccharum officinarum, Secale cereale, Sinapis alba, Solanum Tuberosum), Sorghum bicolor (s. vulgare), Theobroma cacao, Trifolium pratense, Triticale, Triticum aestivum, Triticum durum, Kidney Bean (vicia faba), grape (vi Tis vinifera) with corn (Zea mays).

此外，式I化合物亦可用於因育種(包括基因工程法)而可耐受除草劑作用之作物。In addition, the compounds of formula I can also be used in crops which are tolerant to herbicides by breeding, including genetic engineering methods.

此外，式I化合物亦可用於因育種(包括基因工程法)而可耐受昆蟲或真菌侵害之作物。In addition, the compounds of formula I can also be used in crops which are tolerant to insects or fungi due to breeding, including genetic engineering methods.

此外，式I化合物亦適用於為植物部份植株進行脫水與/或脫葉處理，合適作物植物為棉花、馬鈴薯、油菜、向日葵、大豆或菜豆，特定言之棉花。此時，本發明係有關包含式I化合物(群)，用於植物脫水與/或脫葉處理之組合物、製備此等組合物之方法與植物之脫水與/或脫葉法。In addition, the compounds of the formula I are also suitable for the dehydration and/or defoliation of plant plants, which are cotton, potato, canola, sunflower, soybean or kidney bean, in particular cotton. In this case, the invention relates to compositions comprising the compounds of the formula I (groups), to plant dehydration and/or defoliation treatment, to a process for the preparation of such compositions, to dehydration and/or defoliation of plants.

當式I化合物作為脫水劑時，其特定言之適合脫水作物植株之地上部，如：馬鈴署、油菜、向日葵與大豆，及穀類。此作法可以為此等重要作物植物進行完全機器採收。When the compound of formula I is used as a dehydrating agent, it is specifically suitable for the above-ground parts of dehydrated crop plants, such as: horse ring, rapeseed, sunflower and soybean, and cereals. This practice allows for complete machine harvesting of these important crop plants.

若處理柑桔類、橄欖或其他類果樹，及蘋果類水果、核果及堅果時，經濟上亦有利之作法為可調整落果時間或縮短附著在樹上之時間來緩和採收作業。同樣機轉，亦即促進果實或葉部與植物枝條部份之間形成剝離組織，對完全控有用植物，特定言之棉花之脫葉亦很重要。When dealing with citrus, olive or other fruit trees, and apple fruits, stone fruits and nuts, it is also economically advantageous to adjust the fruit drop time or shorten the time attached to the tree to ease harvesting operations. The same mechanism, that is, to promote the formation of exfoliated tissue between the fruit or the leaves and the branches of the plant, is also important for the complete control of useful plants, specifically the defoliation of cotton.

此外，縮短各棉花植物成熟間隔期亦可提高採收後纖維材料品質。In addition, shortening the maturity interval of each cotton plant can also improve the quality of the fiber material after harvesting.

化合物I或含其之除草組合物可呈例如：現成可用之噴灑水溶液、粉劑、懸浮液，及高濃縮水性、油性或其他懸浮液或勻散液、乳液、油勻散液、糊劑、撒播材料或粒劑型式，利用噴灑法、噴霧法、撒粉法、散播法、澆水法處理或處理種子或與種子混合。使用型式端賴所需目的決定；任何情況下，應確保根據本發明活性成份儘可能完全分佈。The compound I or the herbicidal composition containing the same may be, for example, a ready-to-use spray aqueous solution, a powder, a suspension, and a highly concentrated aqueous, oily or other suspension or leveling liquid, an emulsion, an oil dispersion, a paste, and a spread. In the form of materials or granules, the seeds are treated or treated by spraying, spraying, dusting, spreading, watering or mixing with seeds. The use of the type depends on the desired purpose; in any case, it should be ensured that the active ingredient according to the invention is as completely distributed as possible.

除草組合物包含除草有效量之至少一種式I化合物或I之農業上適用之鹽，與常用於調配作物保護劑之輔助物質。The herbicidal compositions comprise a herbicidally effective amount of at least one agriculturally acceptable salt of a compound of formula I or I, and an auxiliary substance commonly used in the formulation of crop protection agents.

常用於調配作物保護劑之輔助物質實例為惰性輔助物質、固態載劑、界面活性劑(如：勻散劑、保護性膠體、乳化劑、濕化劑與膠黏劑)、有機與無機增稠劑、制細菌劑、防凍劑、消泡劑、可視需要選用之著色劑，及用於種子處理調配物使用之黏著劑。Examples of auxiliary substances commonly used in the formulation of crop protection agents are inert auxiliary substances, solid carriers, surfactants (eg, leveling agents, protective colloids, emulsifiers, humidifiers and adhesives), organic and inorganic thickeners. , bacteriostatic agents, antifreeze agents, defoamers, colorants that can be used as needed, and adhesives used in seed treatment formulations.

增稠劑(亦即改變調配物流動性質之化合物，亦即靜止時高黏度，搖動時則低黏度)實例為多醣如：黃原膠(Kelzanfrom Kelco)、Rhodopol23(Rhone Poulenc)或Veegum(來自R.T.Vanderbilt)及有機與無機植物矽酸鹽如：Attaclay(來自Engelhardt)。Thickeners (ie, compounds that alter the flow properties of the formulation, ie high viscosity at rest, low viscosity when shaken) are examples of polysaccharides such as: xanthan gum (Kelzan) From Kelco), Rhodopol 23 (Rhone Poulenc) or Veegum (from RTVanderbilt) and organic and inorganic plant citrates such as: Attaclay (from Engelhardt).

消泡劑實例為矽乳液(如，例如：SilikonSRE、Wacker或Rhodorsil，來自Rhodia公司)、長鏈醇類、脂肪酸、脂肪酸鹽類、有機氟化合物與其混合物。An example of an antifoaming agent is a hydrazine emulsion (eg, for example: Silikon SRE, Wacker or Rhodorsil From Rhodia, long chain alcohols, fatty acids, fatty acid salts, organofluorine compounds and mixtures thereof.

可使用制菌劑安定水性除草調配物。制菌劑實例為以二氯酚(Diclorophene)與苯甲醇半縮甲醛為主之制菌劑(來自ICI公司之Proxel或來自Thor Chemie公司之ActicideRS與來自Rohm & Haas公司之KathonMK)與異噻唑啉酮衍生物，如：烷基異噻唑啉酮與苯并異噻唑啉酮(Acticide MBS，來自Fa.Thor Chemie公司)。Aqueous formulations can be used to stabilize aqueous herbicidal formulations. An example of a bacteriostat is a bacteriostatic agent based on Diclorophene and benzyl alcohol hemiformal (Proxel from ICI) Or Acticide from Thor Chemie RS and Kathon from Rohm & Haas MK) with isothiazolinone derivatives such as alkylisothiazolinone and benzisothiazolinone (Acticide MBS from Fa. Thor Chemie).

防凍劑實例為乙二醇、丙二醇、尿素或甘油。Examples of antifreeze agents are ethylene glycol, propylene glycol, urea or glycerol.

著色劑實例為難溶於水之色素與可溶於水之染料。可述及之實例為已知下列名稱之染料：若丹明(Rhodamin)B、C.I.色素紅色112號與C.I.溶劑紅色1號，與色素藍色15：4號、色素藍色15：3號、色素藍色15：2號、色素藍色15：1號、色素藍色80號、色素黃色1號、色素黃色13號、色素紅色112號、色素紅色48：2號、色素紅色48：1號、色素紅色57：1號、色素紅色53：1號、色素橙色43號、色素橙色34號、色素橙色5號、色素綠色36號、色素綠色7號、色素白色6號、色素褐色25號、鹼性紫色10號、鹼性紫色49號、酸性紅色51號、酸性紅色52號、酸性紅色14號、酸性藍色9號、酸性黃色23號、鹼性紅色10號、鹼性紅色108號。Examples of colorants are water-insoluble pigments and water-soluble dyes. Examples which may be mentioned are dyes of the following names: Rhodamin B, CI Pigment Red No. 112 and CI Solvent Red No. 1, and Pigment Blue 15:4, Pigment Blue 15:3, Pigment blue 15:2, pigment blue 15:1, pigment blue 80, pigment yellow 1, pigment yellow 13, pigment red 112, pigment red 48:2, pigment red 48:1 , pigment red 57:1, pigment red 53:1, pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, Alkaline purple No. 10, alkaline purple No. 49, acid red No. 51, acid red No. 52, acid red No. 14, acid blue No. 9, acid yellow No. 23, alkaline red No. 10, alkaline red No. 108.

黏著劑實例為聚乙烯基吡咯啶酮、聚乙酸乙烯酯、聚乙烯醇與纖維基醋酸鈉。Examples of the adhesive are polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and cellulose acetate.

合適惰性添加物為例如下列：中沸點至高沸點之礦物油餾份，如：煤油或柴油，及煤焦油與植物性或動物性油、脂系、環系與芳香烴，例如：鏈烷烴、四氫萘、烷化萘或其衍生物、烷化苯或其衍生物，醇類如：甲醇、乙醇、丙醇、丁醇與環己醇，酮類如：環己酮，強極性溶劑例如：胺類如：N－甲基吡咯啶酮，或水。Suitable inert additives are, for example, the following: medium to high boiling mineral oil fractions such as kerosene or diesel, and coal tar with vegetable or animal oils, aliphatic, cyclic and aromatic hydrocarbons, for example: paraffins, four Hydronaphthalene, alkylated naphthalene or its derivatives, alkylated benzene or its derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohexanol, ketones such as cyclohexanone, strong polar solvents such as: Amines such as N-methylpyrrolidone or water.

固態載劑為礦物土，如：矽石、矽膠、矽酸鹽、滑石、高嶺土、石灰石、石灰、白堊、膠塊黏土、黃土、黏土、白雲石、矽藻土、硫酸鈣與硫酸鎂、氧化鎂、研磨之合成材料，肥料如：硫酸銨、磷酸銨、硝酸銨、尿素與植物性產物，如：穀粉、樹皮粉、木屑粉與果殼粉、纖維素粉末與其他固態載劑。The solid carrier is mineral soil, such as: vermiculite, tannin, niobate, talc, kaolin, limestone, lime, chalk, cement clay, loess, clay, dolomite, diatomaceous earth, calcium sulfate and magnesium sulfate, oxidation Magnesium, ground synthetic materials, fertilizers such as: ammonium sulfate, ammonium phosphate, ammonium nitrate, urea and plant products, such as: grain flour, bark powder, wood powder and shell powder, cellulose powder and other solid carrier.

合適界面活性劑(輔劑、濕化劑、膠黏劑、勻散劑與乳化劑)為芳香系磺酸之鹼金屬鹽類、鹼土金屬鹽類與銨鹽類，例如：木質素磺酸(例如：來自Borregaard公司之Borrespers牌產品)－、苯酚磺酸－與萘磺酸(Morwet牌產品，Akzo Nobel公司)－與二丁基萘磺酸(BASF AG公司之Nekal牌產品)－之鹽類，與脂肪酸之鹽類、烷基－與烷基芳基磺酸鹽、烷基硫酸鹽、月桂基醚硫酸鹽與脂肪醇硫酸鹽，與硫酸化十六－、十七－與十八碳烷醇之鹽類，及脂肪醇甘油醚之鹽類，磺酸化萘及其衍生物與甲醛之縮合物、萘或萘磺酸與苯酚及甲醛之縮合物、聚氧伸乙基辛基酚醚、乙氧基化異辛基－、辛基－或壬基酚、烷基苯基或三丁基苯基聚二醇醚、烷基芳基聚醚醇類、異十三碳烷醇、脂肪醇/環氧乙烷縮合物、乙氧基蓖麻油、聚氧乙烯基烷基醚類或聚氧丙烯烷基醚類、月桂基醇聚二醇醚乙酸酯、山梨糖醇酯、木質素亞硫酸鹽廢液與蛋白質、變性蛋白質、多醣(例如：甲基纖維素)、疏水性改質澱粉、聚乙烯醇(來自Clariant公司之Mowiol牌產品)、聚羧酸酯(來自BASF AG公司之Sokolan牌產品)、聚烷氧基化物、聚乙烯基胺(BASF AG之Lupamin牌產品)、聚乙烯亞胺(BASF AG之Lupasol牌產品)、聚乙烯基吡咯啶酮及其共聚物。Suitable surfactants (auxiliaries, wetting agents, adhesives, dispersing agents and emulsifiers) are alkali metal salts, alkaline earth metal salts and ammonium salts of aromatic sulfonic acids, such as: lignosulfonic acid (for example) : Borrespers brand products from Borregaard), phenolsulfonic acid- and naphthalenesulfonic acid (Morwet brand products, Akzo Nobel) - and dibutylnaphthalenesulfonic acid (Nekal brand products of BASF AG) - salts, Salts with fatty acids, alkyl-and alkylarylsulfonates, alkyl sulfates, lauryl ether sulfates and fatty alcohol sulfates, and sulfated c-, hepta- and octadecanols Salts, salts of fatty alcohol glyceryl ethers, condensates of sulfonated naphthalenes and their derivatives with formaldehyde, condensates of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, polyoxyethylene ethyl octyl phenol ether, B Oxylated isooctyl-, octyl- or nonylphenol, alkylphenyl or tributylphenyl polyglycol ether, alkyl aryl polyether alcohols, isotridecyl alcohol, fatty alcohols / Ethylene oxide condensate, ethoxylated castor oil, polyoxyethylene alkyl ether or polyoxypropylene alkyl ether, lauryl alcohol polyglycol ether Ester, sorbitol ester, lignin sulfite waste liquid and protein, denatured protein, polysaccharide (eg methyl cellulose), hydrophobic modified starch, polyvinyl alcohol (Mowiol brand product from Clariant), poly Carboxylic acid ester (Sokolan brand product from BASF AG), polyalkoxylate, polyvinylamine (Lupamin brand product of BASF AG), polyethyleneimine (Lupasol brand product of BASF AG), polyvinylpyrrole Pyridone and its copolymers.

粉劑、撒播材料與細粉製法可共同混合或研磨活性成份與固態載劑製成。The powder, the spreading material and the fine powder method can be mixed or ground together with the active ingredient and the solid carrier.

粒劑，例如：包衣粒劑、浸滲粒劑與均質粒劑可由活性成份與固態載劑結合製成。Granules, for example, coated granules, impregnated granules and homogenous granules can be prepared by combining the active ingredient with a solid carrier.

水性使用型式可由乳液濃縮劑、懸浮液、糊劑、可濕化粉劑或水可勻散性粒劑加水製成。製備乳液、糊劑或油勻散液時，式I或Ia化合物可呈其本身或溶於油或溶劑中，利用濕化劑、膠黏劑、勻散劑或乳化劑，於水中均質化。或者，亦可製備包含活性成份、濕化劑、膠黏劑、勻散劑或乳化劑之濃縮劑，若需要時，可包含適合加水稀釋之溶劑或油。The aqueous use form can be prepared by adding an emulsion concentrate, a suspension, a paste, a wettable powder or a water-dispersible granule to water. When preparing emulsions, pastes or oil dispersions, the compound of formula I or Ia can be homogenized in water by itself or in an oil or solvent, using a wetting agent, an adhesive, a leveling agent or an emulsifier. Alternatively, a concentrate containing an active ingredient, a wetting agent, an adhesive, a leveling agent or an emulsifier may be prepared, and if necessary, a solvent or oil suitable for dilution with water may be included.

現成可用製劑型式之式I化合物濃度可在很大範圍內變化。通常，調配物包含0.001至98%重量比，較佳為0.01至95%重量比之至少一種活性成份。活性成份之使用純度為90%至100%，較佳為95%至100%(依NMR光譜)。The concentration of the compound of formula I in ready-to-use formulations can vary widely. Typically, the formulation will comprise from 0.001 to 98% by weight, preferably from 0.01 to 95% by weight, of at least one active ingredient. The active ingredient is used in a purity of from 90% to 100%, preferably from 95% to 100% (by NMR spectrum).

根據本發明化合物I可例如：依下列方式調配：The compound I according to the invention can, for example, be formulated in the following manner:

1.加水稀釋之產物1. Product diluted with water

A)水溶性濃縮劑取10份重量比活性化合物(群)溶於90份重量比水或水溶性溶劑中。或者，可添加濕化劑或其他輔劑。活性成份於加水稀釋時溶解。依此方式得到活性化合物含量為10%重量比之調配物。A) Water-soluble concentrate A 10 parts by weight of the active compound (group) is dissolved in 90 parts by weight of water or a water-soluble solvent. Alternatively, a wetting agent or other adjuvant may be added. The active ingredient is dissolved when diluted with water. In this way, a formulation having an active compound content of 10% by weight is obtained.

B)勻散性濃縮劑取20份重量比活性化合物(群)溶於添加10份重量比勻散劑(例如：聚乙烯基吡咯啶酮)之70份重量比環己酮中。加水稀釋，製成勻散液。活性化合物含量為20%重量比。B) Leveling concentrate A 20 parts by weight of the active compound (group) is dissolved in 70 parts by weight of cyclohexanone added with 10 parts by weight of a homogenizing agent (for example, polyvinylpyrrolidone). Dilute with water to make a dispersion. The active compound content is 20% by weight.

C)可乳化濃縮劑取15份重量比活性化合物(群)溶於添加十二烷基苯磺酸鈣與蓖麻油乙氧化物(各5份重量比)之75份重量比有機溶劑(例如：烷基芳香系)中。加水稀釋，製成乳液。該調配物之活性化合物含量為15%重量比。C) emulsifiable concentrate 15 parts by weight of active compound (group) dissolved in 75 parts by weight of organic solvent added with calcium dodecylbenzenesulfonate and castor oil ethoxylate (each 5 parts by weight) (for example: In the alkyl aromatic system). Dilute with water to make an emulsion. The formulation has an active compound content of 15% by weight.

D)乳液取25份重量比活性化合物(群)溶於添加十二烷基苯磺酸鈣與蓖麻油乙氧化物(各5份重量比)之35份重量比二甲苯中。利用乳化器(Ultraturrax)添加此混合物至30份重量比水中，製成均勻乳液。加水稀釋，製成乳液。該調配物之活性化合物含量為25%重量比。D) Emulsion 25 parts by weight of the active compound (group) was dissolved in 35 parts by weight of xylene added with calcium dodecylbenzenesulfonate and castor oil ethoxylate (5 parts by weight). This mixture was added to 30 parts by weight of water using an emulsifier (Ultraturrax) to prepare a uniform emulsion. Dilute with water to make an emulsion. The formulation has an active compound content of 25% by weight.

E)懸浮液在攪拌球磨機中添加10份重量比勻散劑與濕化劑，由20份重量比活性化合物(群)與70份重量比水或有機溶劑磨製，形成均勻活性化合物懸浮液。加水稀釋，製成活性化合物之安定懸浮液。該調配物之活性化合物含量為20%重量比。E) Suspension In a stirred ball mill, 10 parts by weight of a homogenizing agent and a wetting agent are added, and 20 parts by weight of the active compound (group) and 70 parts by weight of water or an organic solvent are ground to form a homogeneous active compound suspension. Dilute with water to prepare a stable suspension of the active compound. The formulation has an active compound content of 20% by weight.

F)水可勻散性粒劑與水可溶性粒劑取50份重量比活性化合物(群)，添加50份重量比勻散劑與濕化劑共同細磨，利用機器(例如：擠壓、噴霧嗒、流化床)製成水可勻散性或水可溶性粒劑。加水稀釋，製成活性化合物之安定勻散液或溶液。該調配物之活性化合物含量為50%重量比。F) water-dispersible granules and water-soluble granules, 50 parts by weight of active compound (group), 50 parts by weight of a homogenizing agent and a humidifying agent are finely ground together, using a machine (for example: extrusion, spray 嗒, fluidized bed) made of water-dispersible or water-soluble granules. Dilute with water to prepare a stable solution or solution of the active compound. The formulation has an active compound content of 50% by weight.

G)水可勻散性粉劑與水可溶性粉劑取75份重量比活性化合物(群)於轉鼓式磨粉機(rotor－stator mill)中，添加25份重量比勻散劑、濕化劑與矽膠磨製。加水稀釋，製成活性化合物之安定勻散液或溶液。該調配物之活性化合物含量為75%重量比。G) water-dispersible powder and water-soluble powder, 75 parts by weight of active compound (group) in a rotor-stator mill, adding 25 parts by weight of a homogenizing agent, a humidifying agent and a silicone rubber Grinding. Dilute with water to prepare a stable solution or solution of the active compound. The formulation has an active compound content of 75% by weight.

H)凝膠在攪拌球磨機中，取20份重量比活性化合物(群)，添加10份重量比勻散劑、1份重量比膠凝劑濕化劑與70份重量比水或有機溶劑磨製，製成活性化合物均勻懸浮液。加水稀釋，製成活性化合物之安定懸浮液，藉以得到活性化合物含量為20%重量比之調配物。H) Gel In a stirred ball mill, 20 parts by weight of active compound (group), 10 parts by weight of a homogenizing agent, 1 part by weight of a gelling agent wetting agent and 70 parts by weight of water or an organic solvent are ground. A homogeneous suspension of the active compound is prepared. Diluted with water to prepare a stable suspension of the active compound, whereby a formulation having an active compound content of 20% by weight is obtained.

2.未稀釋即施用之產物2. The product is applied without dilution

I)細粉劑取5份重量比活性化合物(群)磨細，與95份重量比細碎高嶺土均勻混合。製成活性化合物含量為5%重量比之細粉劑。I) The fine powder is finely divided into 5 parts by weight of the active compound (group), and uniformly mixed with 95 parts by weight of finely divided kaolin. A fine powder having an active compound content of 5% by weight is prepared.

J)粒劑(GR、FG、GG、MG)取0.5份重量比活性化合物磨細，與99.5份重量比載劑混合。目前採用擠壓法、噴霧乾燥法或流化床法。製成活性化合物含量為0.5%重量比之未稀釋即可施用之粒劑。J) Granules (GR, FG, GG, MG) were 0.5 parts by weight of the active compound, and mixed with 99.5 parts by weight of the carrier. Extrusion, spray drying or fluidized bed processes are currently used. A granule which can be applied without dilution as an active compound in an amount of 0.5% by weight.

K)ULV溶液(UL)取10份重量比活性化合物(群)溶於90份重量比有機溶劑中，例如：二甲苯。製成活性化合物含量為10%重量比之未稀釋即可施用之產物。K) ULV solution (UL) is taken in 10 parts by weight of the active compound (group) in 90 parts by weight of an organic solvent, such as xylene. The product is applied as an undiluted active compound in an amount of 10% by weight.

下列為確實製成之調配物：I取20份重量比式I化合物溶於由80份重量比烷基化苯、10份重量比8至10莫耳環氧乙烷與1莫耳油酸N－單乙醇醯胺之加合物、5份重量比十二烷基苯磺酸鈣鹽與5份重量比40莫耳環氧乙烷與1莫耳蓖麻油之加合物所組成混合物中。將溶液倒至100 000份重量比水中，均勻分散，製成包含0.02%重量比活性化合物之水性勻散液。The following are prepared formulations: I take 20 parts by weight of the compound of formula I dissolved in 80 parts by weight of alkylated benzene, 10 parts by weight of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid N- An adduct of monoethanolamine, 5 parts by weight of a calcium salt of dodecylbenzenesulfonate and 5 parts by weight of an adduct of 40 moles of ethylene oxide and 1 mole of castor oil. The solution was poured into 100,000 parts by weight of water and uniformly dispersed to prepare an aqueous dispersion containing 0.02% by weight of the active compound.

II取20份重量比式I化合物溶於由40份重量比環己酮、30份重量比異丁醇、20份重量比7莫耳環氧乙烷與1莫耳異辛基酚之加合物及10份重量比40莫耳環氧乙烷與1莫耳蓖麻油之加合物之混合物中。將溶液倒至100 000份重量比水中，均分分散，製成包含0.02%重量比活性化合物之水性勻散液。II. 20 parts by weight of a compound of the formula I dissolved in an adduct of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of 7 moles of ethylene oxide and 1 mole of isooctylphenol And 10 parts by weight of a mixture of 40 moles of ethylene oxide and 1 mole of castor oil adduct. The solution was poured into 100,000 parts by weight of water and dispersed in equal portions to prepare an aqueous dispersion containing 0.02% by weight of the active compound.

III取20份重量比式I化合物溶於由25份重量比環己酮、65份重量比沸點210至280℃之礦物油餾份與10份重量比40莫耳環氧乙烷與1莫耳蓖麻油之加合物所組成混合物中。將溶液倒至100 000份重量比水中，均勻分散，製成包含0.02%重量比活性化合物之水性勻散液。III. 20 parts by weight of the compound of the formula I dissolved in 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction having a boiling point of 210 to 280 ° C and 10 parts by weight of 40 moles of ethylene oxide and 1 mole of hydrazine A mixture of sesame oil adducts. The solution was poured into 100,000 parts by weight of water and uniformly dispersed to prepare an aqueous dispersion containing 0.02% by weight of the active compound.

IV取20份重量比式I化合物與3份重量比二異丁基萘磺酸鈉鹽、17份重量比來自亞硫酸鹽廢液之木質素磺酸鈉鹽及60份重量比矽膠粉末均勻混合，混合物於鎚磨機中磨製。取混合物均勻分佈在20 000份重量比水中，製成包含0.1%重量比活性化合物之噴灑混合物。IV, 20 parts by weight of the compound of the formula I and 3 parts by weight of diisobutylnaphthalenesulfonic acid sodium salt, 17 parts by weight of the sodium ligninsulfonate from the sulfite waste liquid and 60 parts by weight of the silicone powder are uniformly mixed The mixture is ground in a hammer mill. The mixture was uniformly distributed in 20,000 parts by weight of water to prepare a spray mixture containing 0.1% by weight of the active compound.

V取3份重量比式I化合物與97份重量比細碎高嶺土混合。產生包含3%重量比活性化合物之細粉劑。V is a mixture of 3 parts by weight of the compound of formula I and 97 parts by weight of finely divided kaolin. A fine powder comprising 3% by weight of active compound is produced.

VI取20份重量比式I化合物與2份重量比十二烷基苯磺酸鈣、8份重量比脂肪醇聚二醇醚、2份重量比苯酚/尿素/甲醛縮合物之鈉鹽及68份重量比鏈烷烴礦物油均勻混合。產生安定之油性勻散液。VI is 20 parts by weight of the compound of the formula I and 2 parts by weight of calcium dodecylbenzenesulfonate, 8 parts by weight of the fatty alcohol polyglycol ether, 2 parts by weight of the sodium salt of the phenol/urea/formaldehyde condensate and 68 The parts are more homogeneously mixed than the paraffinic mineral oil. Produces a stable oily leveling liquid.

VII取1份重量比式I化合物溶於由70份重量比環己酮、20份重量比乙氧化二異辛基苯酚與10份重量比乙氧基化蓖麻油組成之混合物中。產生安定之乳液濃縮劑。VII is a compound of the formula I dissolved in a mixture of 70 parts by weight of cyclohexanone, 20 parts by weight of diisooctyl ethoxylate and 10 parts by weight of ethoxylated castor oil. Produces a stable emulsion concentrate.

VIII取1份重量比式I化合物溶於由80份重量比己酮與20份重量比WettolEM 31(＝以乙氧基化蓖麻油為主之非離子性乳化劑)組成之混合物中。產生安定之乳液濃縮劑。VIII is taken in 1 part by weight of the compound of formula I dissolved in 80 parts by weight of hexanone and 20 parts by weight of Wettol A mixture of EM 31 (= non-ionic emulsifier based on ethoxylated castor oil). Produces a stable emulsion concentrate.

化合物I或含其之除草組合物可在萌發前或萌發後施用，或與作物植株之種子共同施用。除草組合物或活性化合物之施用法亦可由除草組合物或活性化合物前處理作物植物之種子。若某些作物植物較無法耐受活性成份時，可利用噴灑器具之助，採用噴灑除草組合物之施用技術，以儘可能不與敏感作物植株之葉部接觸之方式，使活性成份可以到達在較低處生長之不要之植物之葉部或無植物之土壤上(後置式(post－directed)、旁置式(lay－by))。Compound I or a herbicidal composition therewith can be applied before or after germination, or co-administered with seeds of crop plants. The method of application of the herbicidal composition or active compound can also pretreat the seed of the crop plant from the herbicidal composition or active compound. If some crop plants are less tolerant to the active ingredient, the application of the herbicidal composition can be carried out by spraying the herbicidal composition, so that the active ingredient can be reached in such a way as not to be in contact with the leaves of the sensitive crop plant as much as possible. On the leaves of plants that are not growing at the lower part or on the soil without plants (post-directed, lay-by).

根據另一項具體實施例，式I化合物與除草組合物之施用法可分別用於處理種子。According to another specific embodiment, the method of application of the compound of formula I and the herbicidal composition can be used to treat the seed, respectively.

種子處理法包括依相關技藝實質上已知之所有技術(種子裹覆法、種子包衣法、種子撒粉法、種子浸泡法、種子膜衣法、種子多層包衣法、種子硬皮包覆法、種子液滴處理法與種子壓片法)，以根據本發明式I化合物與含其之組合物為主之處理法。此時，除草組合物可經稀釋或未稀釋使用。The seed treatment method includes all techniques substantially known in the related art (seed coating method, seed coating method, seed dusting method, seed immersion method, seed film coating method, seed multi-layer coating method, seed hard coating method). , seed droplet treatment method and seed tableting method), the treatment method based on the compound of the formula I according to the invention and the composition containing the same. At this time, the herbicidal composition can be used diluted or undiluted.

"種子"一詞包括所有種類之種子，包括如：穀粒、真種子、果實、球根/塊根、插枝與類似型式。"種子"一詞較佳係指本文中之穀粒與真種子。The term "seed" includes all types of seeds, including, for example, grain, true seeds, fruits, bulbs/roots, cuttings, and the like. The term "seed" preferably refers to the grain and true seeds in this article.

可使用之種子為如上述有用植物之種子及可因轉殖基因或因傳統育種法長成之植物之種子。Seeds which can be used are seeds of useful plants as described above and seeds which can be grown by transgenic genes or by conventional breeding methods.

活性化合物施用率為0.001至3.0，較佳為0.01至1.0公斤/公頃活性物質(a.s.)，端賴控制目標、季節、標的植物與生長階段決定。處理種子時，化合物I之一般施用量為每100公斤種子0.001至10公斤。The active compound application rate is from 0.001 to 3.0, preferably from 0.01 to 1.0 kg/ha of active substance (a.s.), depending on the control target, season, target plant and growth stage. When the seed is treated, the general application rate of the compound I is 0.001 to 10 kg per 100 kg of the seed.

為了擴大作用範圍及達到增效效應，式I化合物可與許多種其他除草性或調節生長性活性成份混合，共同施用。合適混合對象為例如：1,2,4－噻二唑類、1,3,4－噻二唑類、醯胺類、胺基磷酸類與其衍生物、胺基***類、醯基替苯胺類、(雜)芳基氧烷酸類與其衍生物、苯甲酸與其衍生物、苯并噻二酮類、2－芳醯基－1,3－環己二酮類、2－雜芳醯基－1,3－環己二酮類、雜芳基芳基酮類、苯甲基異唑啶酮類、間－CF3 －苯基衍生物、胺甲酸酯類、唑啉羧酸與其衍生物、氯乙醯替苯胺類、環己烯酮肟醚衍生物、二類、二氯丙酸與其衍生物、二氫苯并呋喃、二氫呋喃－3－酮類、二硝基苯胺類、二硝基苯酚類、二苯基醚類、聯吡啶類、鹵羧酸類與其衍生物、脲類、3－苯基尿嘧啶類、咪唑類、咪唑啉酮類、N－苯基－3,4,5,6－四氫酞醯亞胺類、二唑類、環氧乙烷類、苯酚類、芳基氧－與雜芳基氧苯氧基丙酸酯類、苯基乙酸與其衍生物、苯基丙酸與其衍生物、吡唑類、苯基吡唑類、嗒類、吡啶羧酸與其衍生物、嘧啶基醚類、磺醯胺類、磺醯基脲類、三類、三酮類、***啉酮類、***羧醯胺尿嘧啶類、苯基吡唑啉類與異唑啉類與其衍生物。In order to broaden the scope of action and achieve synergistic effects, the compounds of formula I can be combined with a wide variety of other herbicidal or growth-regulating active ingredients for co-administration. Suitable mixing objects are, for example, 1,2,4-thiadiazoles, 1,3,4-thiadiazoles, guanamines, aminophosphoric acids and derivatives thereof, aminotriazoles, mercaptoanilines Classes, (hetero) aryl oxyalkanics and their derivatives, benzoic acid and its derivatives, benzothiazepine Ketones, 2-arylmercapto-1,3-cyclohexanediones, 2-heteroaryl-1,3-cyclohexanediones, heteroaryl aryl ketones, benzylation Azolidinone, m-CF 3 -phenyl derivative, carbamate, oxazolinecarboxylic acid and its derivative, chloroacetate, cyclohexenone oxime ether derivative, Classes, dichloropropionic acid and its derivatives, dihydrobenzofuran, dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyl ethers, bipyridines, halocarboxylic acids And its derivatives, ureas, 3-phenyluracils, imidazoles, imidazolinones, N-phenyl-3,4,5,6-tetrahydrofurfurimides, Diazoles, ethylene oxides, phenols, aryloxy- and heteroaryloxyphenoxypropionates, phenylacetic acid and its derivatives, phenylpropionic acid and its derivatives, pyrazoles, benzene Pyrazoles Classes, pyridinecarboxylic acids and their derivatives, pyrimidinyl ethers, sulfonamides, sulfonyl ureas, three Class, three Ketones, triazolinones, triazole carboxamide uracils, phenylpyrazolines and isoforms Oxazolines and their derivatives.

亦可能有利之作法為單獨施用化合物I或組合其他除草劑施用，或與其他作物保護劑形成混合物施用，例如：與用於控制害蟲或植物病原性真菌或細菌之藥劑共同施用。亦有利之處在於其與無機鹽溶液之相容性，可用於處理微量元素缺乏症。亦可使用其他添加物，如：非植物毒性油類與油濃縮物。It may also be advantageous to administer Compound I alone or in combination with other herbicides, or to form a mixture with other crop protection agents, for example, co-administered with an agent for controlling pests or phytopathogenic fungi or bacteria. It is also advantageous in its compatibility with inorganic salt solutions and can be used to treat trace element deficiency. Other additives such as non-phytotoxic oils and oil concentrates can also be used.

下列實例係說明本發明。The following examples illustrate the invention.

A製備實例A preparation example

產物之判別法係由其於HPLC/MS(高效液相層析法與質譜儀之組合)之滯留時間RT(以分鐘計)、NMR或其熔點(m.p.)判別。The method of discriminating the product is judged by its retention time RT (in minutes), NMR or its melting point (m.p.) in HPLC/MS (combination of high performance liquid chromatography and mass spectrometry).

HPLC管柱：RP－18管柱(Chromolith Speed ROD，來自德國Merck KgaA公司)溶離液：乙腈＋0.1%三氟乙酸(TFA)/水＋0.1%TFA，40℃下，於5分鐘內梯度由5：95至95：5。HPLC column: RP-18 column (Chromolith Speed ROD from Merck KgaA, Germany) Dissolution: acetonitrile + 0.1% trifluoroacetic acid (TFA) / water + 0.1% TFA, at 40 ° C, within 5 minutes The gradient is from 5:95 to 95:5.

MS：四極電噴灑離子化，80 V(正電模式)MS: quadrupole electrospray ionization, 80 V (positive mode)

實例1：3－苯甲基－1,4－二甲基－6－(2－硝基亞苯甲基)哌－2,5－二酮Example 1: 3-Benzyl-1,4-dimethyl-6-(2-nitrophenylene) piperazine -2,5-dione

1.1 2－(第三丁氧基羰基甲基胺基)－3－(2－硝基苯基)－3－三甲基矽烷基氧－丙酸乙酯 於－78℃下，慢慢滴加異丙基胺化鋰溶液(2 M四氫呋喃/正庚烷溶液，46毫升，92毫莫耳)至含(第三丁氧基羰基甲基胺基)乙酸乙酯(20克，92毫莫耳)之THF(無水，50毫升)中。於此溫度下攪拌混合物3小時。慢慢滴加含2－硝基苯甲醛(13.6克，90毫莫耳)之THF(四氫呋喃，無水，30毫升)。於－78℃下攪拌混合物1.5小時後，添加三甲基矽烷基氯(10克，92毫莫耳)。使反應溶液慢慢(12小時)回升至室溫後，於旋轉蒸發器上濃縮。殘質溶於乙酸乙酯，洗滌，脫水與濃縮。依此方式所得殘質再經管柱層析法純化(SiO2 ，己烷/乙酸乙酯)。產生7.1克(18%)非極性異構物，即用於下一個反應步驟。1.1 2-(Tertibutoxycarbonylmethylamino)-3-(2-nitrophenyl)-3-trimethyldecyloxy-propionic acid ethyl ester Lithium isopropylamide solution (2 M tetrahydrofuran/n-heptane solution, 46 ml, 92 mmol) was added dropwise at -78 ° C to (tris-butoxycarbonylmethylamino)acetic acid. Ethyl ester (20 g, 92 mmol) in THF (anield, 50 mL). The mixture was stirred at this temperature for 3 hours. 2-Nitrobenzaldehyde (13.6 g, 90 mmol) in THF (tetrahydrofuran, anhydrous, 30 mL) was slowly added dropwise. After the mixture was stirred at -78 ° C for 1.5 hours, trimethylsulfonyl chloride (10 g, 92 mmol) was added. The reaction solution was allowed to warm to room temperature slowly (12 hours) and then concentrated on a rotary evaporator. The residue was dissolved in ethyl acetate, washed, dried and concentrated. The residue obtained in this manner was purified by column chromatography (SiO 2 , hexane / ethyl acetate). 7.1 g (18%) of the non-polar isomer was produced, which was used in the next reaction step.

M＋Na(m/z)：463。M+Na (m/z): 463.

1.2 3－羥基－2－甲基胺基－3－(2－硝基苯基)丙酸乙酯 1.2 3-Hydroxy-2-methylamino-3-(2-nitrophenyl)propanoic acid ethyl ester

添加三氟乙酸(20毫升)至2－(第三丁氧基羰基甲基胺基)－3－(2－硝基苯基)－3－三甲基矽烷基氧丙酸乙酯(8.6克，19.5毫莫耳)之CH2 Cl2 (100毫升)溶液中，於室溫下攪拌混合物12小時。混合物經NaHCO3 溶液(飽和)中和，分相，與濃縮。取依此方式所得殘質經管柱層析法純化(SiO2 ，己烷/乙酸乙酯)。產生1.7克(32%)目標化合物之淺黃色固體。Add trifluoroacetic acid (20 ml) to ethyl 2-(t-butoxycarbonylmethylamino)-3-(2-nitrophenyl)-3-trimethyldecyloxypropanoate (8.6 g The mixture was stirred at room temperature for 12 hours in a solution of 19.5 mmol of CH 2 Cl 2 (100 mL). The mixture was neutralized with a NaHCO 3 solution (saturated), phase separated and concentrated. The residue obtained in this manner was purified by column chromatography (SiO 2 , hexane / ethyl acetate). A pale yellow solid of 1.7 g (32%) of desired compound was obtained.

M＋1(m/z)：269。M+1 (m/z): 269.

1.3 2－{[2－(第三丁氧基羰基甲基胺基)－3－苯基丙醯基]甲基胺基}－3－羥基－3－(2－硝基苯基)丙酸乙酯 1.3 2-{[2-(Tertibutoxycarbonylmethylamino)-3-phenylpropanyl]methylamino}-3-hydroxy-3-(2-nitrophenyl)propanoic acid Ethyl ester

取3－羥基－2－甲基胺基－3－(2－硝基苯基)丙酸乙酯(1.7克，6.3毫莫耳)、2－(第三丁氧基羰基甲基胺基)－3－苯基丙酸(2克，7毫莫耳)、N－乙基二異丙基胺(4.5克，35毫莫耳)與EDAC(3克，15.6毫莫耳)於THF(無水，50毫升)中攪拌3天。反應溶液於旋轉蒸發器上濃縮。殘質溶於乙酸乙酯，所得溶液經洗滌，脫水與濃縮。產生2.1克(63%)目標化合物之淺黃色油。Take ethyl 3-hydroxy-2-methylamino-3-(2-nitrophenyl)propanoate (1.7 g, 6.3 mmol), 2-(t-butoxycarbonylmethylamino) 3-phenylpropionic acid (2 g, 7 mmol), N-ethyldiisopropylamine (4.5 g, 35 mmol) and EDAC (3 g, 15.6 mmol) in THF Stir in 50 ml) for 3 days. The reaction solution was concentrated on a rotary evaporator. The residue was dissolved in ethyl acetate and the resulting solution was washed, dried and concentrated. A pale yellow oil of 2.1 g (63%) of desired compound was obtained.

M＋1(m/z)：530。M+1 (m/z): 530.

1.4 3－羥基－2－[甲基－(2－甲基胺基－3－苯基丙醯基)胺基]－3－(2－硝基苯基)丙酸乙酯 1.4 3-Hydroxy-2-[methyl-(2-methylamino-3-phenylpropanyl)amino]-3-(2-nitrophenyl)propanoic acid ethyl ester

添加三氟乙酸(10毫升)至2－{[2－(第三丁氧基羰基甲基胺基)－3－苯基丙醯基]甲基胺基}－3－羥基－3－(2－硝基苯基)丙酸乙酯(2.1克，3.9毫莫耳)之CH2 Cl2 (20毫升)溶液中，於室溫下攪拌混合物2小時後，於旋轉蒸發器上濃縮。取依此方式所得殘質作為進行下一個步驟之粗產物。Add trifluoroacetic acid (10 ml) to 2-{[2-(t-butoxycarbonylmethylamino)-3-phenylpropenyl]methylamino}-3-hydroxy-3-(2) - nitrophenyl) propionate (2.1 g, 3.9 mmol) of CH 2 Cl 2 (20 mL), the mixture stirred at room temperature for 2 hours, concentrated on a rotary evaporator. The residue obtained in this manner was taken as the crude product for the next step.

1.5 3－苯甲基－6－[羥基－(2－硝基苯基)甲基]－1,4－二甲基哌－2,5－二酮 1.5 3-Benzyl-6-[hydroxy-(2-nitrophenyl)methyl]-1,4-dimethylperidine -2,5-dione

取1.4所得殘質溶於THF(50毫升)，添加NH4 OH(25%水溶液，10毫升)。於室溫下攪拌混合物12小時。添加H2 O(100毫升)後，以甲基第三丁基醚萃取混合物，有機相脫水與濃縮。取依此方式所得殘質經管柱層析法純化(SiO2 ，己烷/乙酸乙酯)。產生0.57克(38%)極性異構物，再用於下一個步驟。Take the resulting residue was dissolved in 1.4 THF (50 mL) was added NH 4 OH (25% aq, 10 ml). The mixture was stirred at room temperature for 12 hours. After addition of H 2 O (100 mL), the mixture was extracted with methyl t-butyl ether and the organic phase was dried and concentrated. The residue obtained in this manner was purified by column chromatography (SiO 2 , hexane / ethyl acetate). 0.57 g (38%) of the polar isomer was produced and used in the next step.

M＋1(m/z)：384。M+1 (m/z): 384.

1.6甲磺酸(5－苯甲基－1,4－二甲基－3，6－二氧代哌－2－基)－(2－硝基苯基)甲酯 1.6 methanesulfonic acid (5-benzyl-1,4-dimethyl-3,6-dioxopiperine -2-yl)-(2-nitrophenyl)methyl ester

添加DMAP(1.8克，14.7毫莫耳)與甲磺醯氯(30毫升)至含3－苯甲基－6－[羥基－(2－硝基苯基)甲基]－1,4－二甲基哌－2,5－二酮(5.5克，14.3毫莫耳)之吡啶(100毫升)中，於室溫下攪拌混合物12小時後，於旋轉蒸發器上濃縮。添加H2 O與CH2 Cl2 ，採用吸濾法過濾排出不可溶之黑色樹脂，分相，有機相濃縮。取依此方式所得殘質經管柱層析法純化(SiO2 ，己烷/乙酸乙酯)。產生5.1克(77%)目標化合物之淺黃色泡沫狀物。Add DMAP (1.8 g, 14.7 mmol) with methanesulfonium chloride (30 mL) to 3-benzyl-6-[hydroxy-(2-nitrophenyl)methyl]-1,4-di Methylpiper -2,5-Dione (5.5 g, 14.3 mmol) in pyridine (100 mL). H 2 O and CH 2 Cl 2 were added , and the insoluble black resin was filtered by suction filtration, and the phases were separated, and the organic phase was concentrated. Purified by column chromatography of the residue so obtained manner (SiO 2, hexane / ethyl acetate). A pale yellow foam of 5.1 g (77%) of title compound was obtained.

M＋1(m/z)：462。M+1 (m/z): 462.

1.7 3－苯甲基－1,4－二甲基－6－(2－硝基亞苯甲基)哌－2,5－二酮於0℃下，慢慢滴加DBU(1.4克，9毫莫耳)至含甲磺酸(5－苯甲基－1,4－二甲基－3,6－二氧代哌－2－基)－(2－硝基苯基)甲酯(4.25克，9毫莫耳)之THF(100毫升)中，於0℃下攪拌混合物4小時。於此溫度下，使用檸檬酸(10%)調整pH至7，然後使混合物慢慢回升至室溫。添加H2 O與乙酸乙酯後，分相，有機相濃縮。取依此方式所得殘質經管柱層析法純化(SiO2 ，甲基第三丁基醚/乙酸乙酯)。產生2.5克(76%)目標化合物之黃色泡沫狀物。1.7 3-Benzyl-1,4-dimethyl-6-(2-nitrophenylene) piperazine -2,5-dione at 0 ° C, slowly add DBU (1.4 g, 9 mmol) to methanesulfonic acid (5-benzyl-1,4-dimethyl-3,6- Dioxetane The mixture was stirred at 0 ° C for 4 hours in THF (100 mL). At this temperature, the pH was adjusted to 7 using citric acid (10%), and then the mixture was slowly allowed to warm to room temperature. After addition of H 2 O and ethyl acetate, the phases were separated and the organic phase was concentrated. The residue obtained in this manner was purified by column chromatography (SiO 2 , methyl t-butyl ether / ethyl acetate). A yellow foam of 2.5 g (76%) of title compound was obtained.

取依此方式所得Z ：E 異構物混合物經製備性MPLC分離(矽膠：Merck Lichroprep RP－18(40－63 μm)，MeOH：H2 O＝60：40)。分離之異構物之1 H－NMR(CDCl3 )：a)δ＝2.62(s,3H),3.09(s,3H),3.23(m,2H),4.39(m,1H),6.39(d,1H),7.13(s,1H),7.17(m,1H),7.24(m,1H),7.32(m,2H),7.44(m,1H),7.49(m,1H),8.05(d,2H)。The Z : E isomer mixture obtained in this manner was separated by preparative MPLC (silicone: Merck Lichroprep RP-18 (40-63 μm), MeOH: H 2 O = 60:40). 1 H-NMR (CDCl 3 ) of the isolated isomer: a) δ = 2.62 (s, 3H), 3.09 (s, 3H), 3.23 (m, 2H), 4.39 (m, 1H), 6.39 (d) , 1H), 7.13 (s, 1H), 7.17 (m, 1H), 7.24 (m, 1H), 7.32 (m, 2H), 7.44 (m, 1H), 7.49 (m, 1H), 8.05 (d, 2H).

b)δ＝2.91(s,3H),3.15(dm,1H),3.33(s,3H),3.29(dm,1H),4.32(m,1H),6.28(s,1H),6.75(m,1H),7.08(m,2H),7.32(m,3H),7.39(m,1H),7.47(m,1H),8.04(d,1H)。b) δ = 2.91 (s, 3H), 3.15 (dm, 1H), 3.33 (s, 3H), 3.29 (dm, 1H), 4.32 (m, 1H), 6.28 (s, 1H), 6.75 (m, 1H), 7.08 (m, 2H), 7.32 (m, 3H), 7.39 (m, 1H), 7.47 (m, 1H), 8.04 (d, 1H).

實例105/106：3－苯甲基－1,4－二甲基－6－(2－噻唑－2－基亞苯甲基)－哌－2,5－二酮Example 105/106: 3-Benzyl-1,4-dimethyl-6-(2-thiazol-2-ylbenzylidene)-piper -2,5-dione

添加600毫克3－苯甲基－1,4－二甲基－6－(2－碘亞苯甲基)－哌－2,5－二酮(實例4，依據實例1製備)、250毫克雙(二亞苯甲基丙酮)鈀與500毫克三苯基胂(arsan)與30毫升二烷至氬蒙氣下之反應瓶中。添加1克2－(三丁基錫烷基)噻唑，加熱至60℃ 16小時。反應混合物真空濃縮，殘質經矽膠，使用己烷/甲基－第三丁基醚(2：1 v/v)層析。依此方式得到404毫克蠟狀固體。Add 600 mg of 3-benzyl-1,4-dimethyl-6-(2-iodobenzylidene)-per pipe -2,5-dione (Example 4, prepared according to Example 1), 250 mg of bis(diphenyleneacetone)palladium and 500 mg of triphenylsulfonium (arsan) with 30 ml of two Alkane to argon atmosphere in the reaction flask. 1 g of 2-(tributylstannyl)thiazole was added and heated to 60 ° C for 16 hours. The reaction mixture was concentrated in vacuo and the residue was purified eluting eluting eluting In this way, 404 mg of a waxy solid was obtained.

實例115：3－苯甲基－1,4－二甲基－6－(2－氰基－5,6－二氟亞苯甲基)－哌－2,5－二酮Example 115: 3-Benzyl-1,4-dimethyl-6-(2-cyano-5,6-difluorobenzylidene)-peri -2,5-dione

在反應瓶中添加2.0克3－苯甲基－1,4－二甲基－6－(2－溴－5,6－二氟亞苯甲基)－哌－2,5－二酮(實例119，依據實例11製備)，於155℃與氬蒙氣下，與1.7克氰化亞銅(I)，於50毫升N－甲基吡咯啶酮中反應18小時。反應混合物真空濃縮，殘質溶於乙酸乙酯，所得溶液經水洗滌3次，脫水，再真空濃縮一次。殘質經矽膠，使用己烷/乙酸乙酯(1：1 v/v)層析。依此方式得到331毫克Z－異構物之淺黃色固體，熔點為175℃，及310毫克E－異構物米色固體，熔點205℃。Add 2.0 g of 3-benzyl-1,4-dimethyl-6-(2-bromo-5,6-difluorobenzylidene)-piper to the reaction flask -2,5-dione (Example 119, prepared according to Example 11), reacted with 1.7 g of cuprous cyanide (I) in 50 mL of N-methylpyrrolidone at 155 ° C under argon atmosphere. hour. The reaction mixture was concentrated in vacuo. The residue was chromatographed using hexane/ethyl acetate (1:1 v/v). In this way, 331 mg of the Z-isomer was obtained as a pale yellow solid, m.p.

下表2、3與4所列化合物與下表5所列化合物係依類似方式製備(實例2至214)。The compounds listed in Tables 2, 3 and 4 below were prepared in a similar manner to the compounds listed in Table 5 below (Examples 2 to 214).

Exp.# 實例編號m.p. 熔點Ph 苯基i－Pr 異丙基 Exp.# Example number mp Melting point Ph phenyl i-Pr isopropyl

表3： EXp.# 實例編號m.p. 熔點table 3: EXp.# instance number mp melting point

Exp.# 實例編號m.p. 熔點 Exp.# Example number mp melting point

表5： Exp.# 實例編號m.p. 熔點table 5: Exp.# Example number mp melting point

B項：應用實例Item B: Application examples

以溫室試驗證實式I化合物之除草活性：所採用之培養容器為含約3.0%腐殖土作為基質之砂質壤土之塑膠花盆。分開播種各試驗植物品種之種子。The herbicidal activity of the compound of formula I was confirmed by a greenhouse test: the culture vessel used was a plastic flowerpot containing sandy soil of about 3.0% humus as a substrate. Seeds of each test plant variety were sown separately.

進行萌發前處理時，取已於水中懸浮或乳化之活性成份，利用均勻分佈之噴嘴直接在播種後施用。稍微在容器中灌水，促進發芽與生長，隨後覆上透明塑膠套，直到植物發根為止。該覆蓋法可使試驗植物均勻發芽，除非受到活性成份破壞。In the pre-emergence treatment, the active ingredient suspended or emulsified in water is taken and applied directly after sowing using a uniformly distributed nozzle. Slightly fill the container to promote germination and growth, then cover with a clear plastic cover until the roots of the plant. The covering method allows the test plants to germinate evenly unless destroyed by the active ingredient.

進行萌發後處理時，先使試驗植物長至高3至15公分，端賴植物習性決定，然後以於水中懸浮或乳化之活性成份處理。因此可直接播種試驗植物並於同一容器中生長，或可先長成幼苗後，再於處理前幾天移植至試驗容器中。For post-emergence treatment, the test plants are first grown to a height of 3 to 15 cm, depending on the habit of the plant, and then treated with the active ingredient suspended or emulsified in water. Therefore, the test plants can be directly sown and grown in the same container, or can be grown into seedlings and transplanted into the test container a few days before the treatment.

依品種而定，植物保留在10－25℃或20－35℃下。試驗期長達2至4週。此期間，照顧植物並評估各處理之反應。Depending on the variety, the plants are kept at 10-25 ° C or 20-35 ° C. The test period is as long as 2 to 4 weeks. During this period, take care of the plants and assess the response of each treatment.

採用0至100級分進行評估。100分表示沒有植物萌發，或至少完全破壞地上部份，0表示沒有損傷，或生長過程正常。至少70級分相當於良好之除草活性，至少85級分相當於極佳之除草活性。Evaluation was performed using 0 to 100 fractions. A score of 100 indicates that no plant germinates, or at least completely destroys the aerial part, with 0 indicating no damage or normal growth. At least 70 fractions correspond to good herbicidal activity and at least 85 fractions correspond to excellent herbicidal activity.

溫室實驗所使用之植物屬於下列品種： The plants used in the greenhouse experiments belong to the following varieties:

實例編號1、13、16、44、47、48、49、51、52、129、132、160與170之化合物當依萌發後處理法施用時，展現良好至極佳之除草活性。The compounds of Examples Nos. 1, 13, 16, 44, 47, 48, 49, 51, 52, 129, 132, 160 and 170 exhibited good to excellent herbicidal activity when applied by post-emergence treatment.

當進行萌發後處理法，以3公斤/公頃施用率施用實例44與160化合物時，其對ABUTH展現良好除草活性。When the post-emergence treatment was carried out, the compounds of Examples 44 and 160 were applied at a rate of 3 kg/ha, which exhibited good herbicidal activity against ABUTH.

當進行萌發後處理法，以1公斤/公頃施用率施用實例1、16與129化合物時，對AMARE展現極佳除草活性。當進行萌發後處理法，以0.5公斤/公頃施用率施用實例13化合物時，對AMARE展現極佳除草活性。When the post-emergence treatment was carried out, the compounds of Examples 1, 16 and 129 were applied at an application rate of 1 kg/ha, and exhibited excellent herbicidal activity against AMARE. When the post-emergence treatment was carried out, the compound of Example 13 was applied at an application rate of 0.5 kg/ha, and the AMARE exhibited excellent herbicidal activity.

當進行萌發後處理法，以3公斤/公頃施用率施用實例132化合物時，對AVEFA展現極佳除草活性。When the post-emergence treatment was carried out, the compound of Example 132 was applied at an application rate of 3 kg/ha, which exhibited excellent herbicidal activity against AVEFA.

當進行萌發後處理法，以1公斤/公頃施用率施用實例1化合物時，對LOLMU展現極佳除草活性。When the post-emergence treatment was carried out, the compound of Example 1 was applied at an application rate of 1 kg/ha, and showed excellent herbicidal activity against LOLMU.

當進行萌發後處理法，以3公斤/公頃施用率施用實例44、47/48(混合物)、49、51與160化合物時，對SETFA展現極佳除草活性，且實例52與132化合物對SETFA展現良好除草活性。當進行萌發後處理法，以1公斤/公頃施用率施用實例170化合物時，對SETFA展現極佳除草活性。When the post-emergence treatment was carried out, the examples 44, 47/48 (mixture), 49, 51 and 160 compounds were applied at a rate of 3 kg/ha, which showed excellent herbicidal activity against SETFA, and the examples 52 and 132 compounds exhibited for SETFA. Good herbicidal activity. When the post-emergence treatment was carried out, the compound of Example 170 was applied at an application rate of 1 kg/ha, which exhibited excellent herbicidal activity against SETFA.

實例編號38、40、45、54、62、73、100、101、109、110、119、124、137、140、147、148、191、198、204、206與214之化合物當依萌發前處理法施用時，展現良好至極佳除草活性。Compounds of Examples Nos. 38, 40, 45, 54, 62, 73, 100, 101, 109, 110, 119, 124, 137, 140, 147, 148, 191, 198, 204, 206, and 214 are treated as pre-emergence When applied, it exhibits good to excellent herbicidal activity.

當進行萌發前處理法，以3公斤/公頃施用率施用實例73化合物時，其對ABUTH展現良好除草活性。When the pre-emergence treatment was carried out, the compound of Example 73 was applied at a rate of 3 kg/ha, which exhibited good herbicidal activity against ABUTH.

當進行萌發前處理法，以1公斤/公頃施用率施用實例137化合物時，其對AMARE展現良好除草活性。When the pre-emergence treatment was carried out, the compound of Example 137 was applied at a rate of 1 kg/ha, which exhibited good herbicidal activity against AMARE.

當進行萌發前處理法，以1公斤/公頃施用率施用實例206化合物時，其對AVEFA展現良好除草活性。When the pre-emergence treatment was carried out, the compound of Example 206 was applied at a rate of 1 kg/ha, which exhibited good herbicidal activity against AVEFA.

當進行萌發前處理法，以1公斤/公頃施用率施用實例38、45、54、124、140、147與198化合物時，其對APSEV展現極佳除草活性。當進行萌發前處理法，以0.5公斤/公頃施用率施用實例119與191化合物時，其對APSEV展現良好除草活性。When the pre-emergence treatment was carried out, the compounds of Examples 38, 45, 54, 124, 140, 147 and 198 were applied at an application rate of 1 kg/ha, which exhibited excellent herbicidal activity against APSEV. When the pre-emergence treatment was carried out, the compounds of Examples 119 and 191 were applied at an application rate of 0.5 kg/ha, which exhibited good herbicidal activity against APSEV.

當進行萌發前處理法，以1公斤/公頃施用率施用實例38、45、100/101(混合物)與109/110(混合物)化合物時，其對ECHCG展現極佳除草活性，且化合物147對ECHCG展現良好除草活性。進行萌發前處理法，以3公斤/公頃施用率施用實例40與204化合物時，對ECHCG展現極佳除草活性，且實例206化合物對ECHCG展現良好除草活性。When the pre-emergence treatment was carried out, the examples 38, 45, 100/101 (mixture) and 109/110 (mixture) were applied at a rate of 1 kg/ha, which showed excellent herbicidal activity against ECHCG, and compound 147 against ECHCG. Shows good herbicidal activity. The pre-emergence treatment was carried out, and the application of the compounds of Examples 40 and 204 at an application rate of 3 kg/ha exhibited excellent herbicidal activity against ECHCG, and the compound of Example 206 exhibited good herbicidal activity against ECHCG.

當進行萌發前處理法，以1公斤/公頃施用率施用實例109/110(混合物)與140化合物時，對SETFA展現極佳除草活性。當進行萌發前處理法，以3公斤/公頃施用率施用實例62化合物時，及以2公斤/公頃施用率施用實例206化合物時，分別對SETFA展現良好除草活性。When the pre-emergence treatment was carried out, the examples 109/110 (mixture) and 140 compounds were applied at an application rate of 1 kg/ha, which showed excellent herbicidal activity against SETFA. When the pre-emergence treatment was carried out, the compound of Example 62 was applied at an application rate of 3 kg/ha, and the compound of Example 206 was applied at an application rate of 2 kg/ha, respectively, exhibited good herbicidal activity against SETFA.

當進行萌發前處理法，以1公斤/公頃施用率施用實例100/101(混合物)化合物時，其對SETIT展現極佳除草活性。當進行萌發前處理法，以3公斤/公頃施用率施用實例40與204化合物時，對SETIT展現極佳除草活性。當進行萌發前處理法，以3公斤/公頃施用率施用實例214化合物時，其對SETIT展現良好除草活性。When the pre-emergence treatment was carried out, the example 100/101 (mixture) compound was applied at an application rate of 1 kg/ha, which exhibited excellent herbicidal activity against SETIT. When the pre-emergence treatment was carried out, the compounds of Examples 40 and 204 were applied at an application rate of 3 kg/ha, which exhibited excellent herbicidal activity against SETIT. When the pre-emergence treatment was carried out, the compound of Example 214 was applied at a rate of 3 kg/ha, which exhibited good herbicidal activity against SETIT.

Claims (13)

一種以式I哌化合物或式I哌化合物之農業上適用之鹽作為除草劑之用途， 其中式I之代號定義如下：R1 為：C1 -C6 -烷基、C3 -C6 -環烷基、苯基-(C1 -C6 )-烷基、雜環基-(C1 -C6 )-烷基；苯基-[C1 -C6 -烷氧基羰基]-(C1 -C6 )-烷基或苯基雜環基-(C1 -C6 )-烷基；或COR21 ，其中R21 為氫、C1 -C6 -烷基、C3 -C6 -環烷基、C1 -C6 -烷氧基、苯基或萘基；或OR24 ，其中R24 為C1 -C6 -烷基；其中R1 之取代基之如上述脂系、環狀或芳族基團可部份或完全鹵化與/或可帶有1至3個下列基團：氰基、羥基、C1 -C4 -烷基、C1 -C4 -鹵烷基、C3 -C6 -環烷基、C1 -C4 -烷氧基、C1 -C4 -烷基硫、[二-(C1 -C4 )-烷基]胺基、C1 -C4 -烷基羰基、羥基羰基、C1 -C4 -烷氧基羰基、胺基羰基、C1 -C4 -烷基胺基羰基、[二-(C1 -C4 )-烷基]胺基羰基或C1 -C4 -烷基羰基氧； 且其中R1 亦可為氫；R2 為C1 -C6 -烷基；R3 為氫或鹵素；R4 、R5 、R6 分別獨立為氫或C1 -C6 -烷基；A1 為苯基、吡啶基或噻吩基；A2 為苯基；Ra 為鹵素、氰基、硝基、C1 -C6 -烷基、C3 -C6 -環烷基、C2 -C6 -烯基、C3 -C6 -環烯基、C4 -C10 -烷二烯基、C2 -C6 -炔基、[三-(C1 -C6 )-烷基矽烷基]-(C2 -C6 )-炔基、C3 -C6 -環炔基、C1 -C6 -烷基硫、苯基-(C1 -C6 )-烷基、苯基-(C2 -C6 )-烯基、苯基磺醯基-(C1 -C6 )-烷基、雜環基-(C1 -C6 )-烷基或苯基-[C1 -C6 -烷氧基羰基]-(C1 -C6 )-烷基，具有6至14員環之單環或多環芳族碳環或具有1、2、3或4個選自氧、硫與氮所組成群中相同或相異雜原子作為環組員之5-或6-員雜芳基，其可利用碳或氮附接且可再與苯環稠合，或5-至6-員雜芳環可形成雙環系統，其中雜芳基為具有3或多個環原子之單環-或雙環飽和、部份不飽和或芳族雜環，或Z3 COR11 ，其中R11 為氫、C1 -C6 -烷基、C3 -C6 -環烷基或C1 -C6 -烷氧基；且其中Z3 為一鍵結、-CH2 -或-CH2 -CH2 -；且其中Ra 取代基之如上述脂族、環狀或芳族基團可部份或完全鹵化及/或可帶有1至3個下列基團：氰基、羥基、C1 -C4 -烷基、C1 -C4 -鹵烷基、C3 -C6 -環烷基、C1 - C4 -烷氧基、C1 -C4 -鹵烷氧基、C1 -C4 -烷基硫、[二-(C1 -C4 )-烷基]胺基、C1 -C4 -烷基羰基、羥基羰基、C1 -C4 -烷氧基羰基、胺基羰基、C1 -C4 -烷基胺基羰基、[二-(C1 -C4 )-烷基]胺基羰基或C1 -C4 -烷基羰基氧；且Ra 係附接在A1 附接點之鄰位；Rb 與Rc 分別獨立為氫、鹵素或C1 -C6 -烷基；且Rd 、Re 或Rf 為氫。Piper of formula I Compound or formula I The use of the agriculturally applicable salt of the compound as a herbicide, Wherein the code of formula I is defined as follows: R 1 is: C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, phenyl-(C 1 -C 6 )-alkyl, heterocyclyl-( C 1 -C 6 )-alkyl; phenyl-[C 1 -C 6 -alkoxycarbonyl]-(C 1 -C 6 )-alkyl or phenylheterocyclyl-(C 1 -C 6 ) -alkyl; or COR 21 , wherein R 21 is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl, C 1 -C 6 -alkoxy, phenyl or naphthyl; OR 24 , wherein R 24 is C 1 -C 6 -alkyl; wherein the substituent of R 1 such as the above aliphatic, cyclic or aromatic group may be partially or fully halogenated and/or may have 1 to 3 The following groups: cyano, hydroxy, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl, C 3 -C 6 -cycloalkyl, C 1 -C 4 -alkoxy, C 1- C 4 -alkylthio, [di-(C 1 -C 4 )-alkyl]amino, C 1 -C 4 -alkylcarbonyl, hydroxycarbonyl, C 1 -C 4 -alkoxycarbonyl, An aminocarbonyl group, a C 1 -C 4 -alkylaminocarbonyl group, a [di-(C 1 -C 4 )-alkyl]aminocarbonyl group or a C 1 -C 4 -alkylcarbonyloxy group; and wherein R 1 is also can be hydrogen; R 2 is a C 1 -C 6 - alkyl; R 3 is hydrogen or halogen; R 4, R 5, R 6 are each independently hydrogen or C 1 -C 6 - alkyl; A 1 is benzene , Pyridyl or thienyl group; A 2 is a phenyl group; R a is halogen, cyano, nitro, C 1 -C 6 - alkyl, C 3 -C 6 - cycloalkyl, C 2 -C 6 - alkenyl , C 3 -C 6 -cycloalkenyl, C 4 -C 10 -alenadienyl, C 2 -C 6 -alkynyl, [tri-(C 1 -C 6 )-alkyldecylalkyl]-( C 2 -C 6 )-alkynyl, C 3 -C 6 -cycloalkynyl, C 1 -C 6 -alkylthio, phenyl-(C 1 -C 6 )-alkyl, phenyl-(C 2 -C 6 )-alkenyl, phenylsulfonyl-(C 1 -C 6 )-alkyl, heterocyclyl-(C 1 -C 6 )-alkyl or phenyl-[C 1 -C 6 - Alkoxycarbonyl]-(C 1 -C 6 )-alkyl, a monocyclic or polycyclic aromatic carbocyclic ring having 6 to 14 membered rings or having 1, 2, 3 or 4 selected from the group consisting of oxygen, sulfur and nitrogen The 5- or 6-membered heteroaryl group of the same or different heteroatoms in the group as a ring member, which may be attached by carbon or nitrogen and may be fused to the benzene ring, or 5- to 6-membered heteroaryl The ring may form a bicyclic ring system wherein the heteroaryl group is a monocyclic or bicyclic saturated, partially unsaturated or aromatic heterocyclic ring having 3 or more ring atoms, or Z 3 COR 11 wherein R 11 is hydrogen, C 1 -C 6 -alkyl, C 3 -C 6 -cycloalkyl or C 1 -C 6 -alkoxy; and wherein Z 3 is a bond, -CH 2 - or -CH 2 -CH 2 -; wherein R a and the substituents are as described above, aliphatic, cyclic or aromatic radicals may be partially or fully halogenated and / or may carry one to three of the following groups: cyano, hydroxyl, C 1 -C 4 - alkyl, C 1 -C 4 - haloalkyl, C 3 -C 6 - cycloalkyl, C 1 - C 4 - alkoxy, C 1 -C 4 - haloalkoxy, C 1- C 4 -alkylthio, [di-(C 1 -C 4 )-alkyl]amino, C 1 -C 4 -alkylcarbonyl, hydroxycarbonyl, C 1 -C 4 -alkoxycarbonyl, Aminocarbonyl, C 1 -C 4 -alkylaminocarbonyl, [di-(C 1 -C 4 )-alkyl]aminocarbonyl or C 1 -C 4 -alkylcarbonyloxy; and R a attached Adjacent to the A 1 attachment point; R b and R c are each independently hydrogen, halogen or C 1 -C 6 -alkyl; and R d , R e or R f is hydrogen. 如請求項1之式I哌化合物之用途，其中A1 為苯基或吡啶基。As in the case of claim 1 Use of a compound wherein A 1 is phenyl or pyridyl. 如請求項1之式I哌化合物之用途，其中：Ra 係選自下列基團所組成群中：鹵素、氰基、硝基、C1 -C6 -烷基、C2 -C6 -烯基、C2 -C6 -炔基、C3 -C6 -環烷基、[三-(C1 -C6 )-烷基矽烷基]-C2 -C6 -炔基、Z3 COR11 、C1 -C6 -烷基硫、具有6至14員環之單環或多環芳族碳環或雜芳基，該雜芳基為3或多個環原子之單環-或雙環飽和、部份不飽和或芳族雜環，其中Z3 為一鍵結且R11 為氫、C1 -C6 -烷基或C1 -C6 -烷氧基；或Rb 與Rc 分別獨立為氫，且其中取代基Ra 之如上述脂族、環狀或芳族基團可部份或完全鹵化。As in the case of claim 1 The use of the compound, wherein: R a is selected from the group consisting of halogen, cyano, nitro, C 1 -C 6 -alkyl, C 2 -C 6 -alkenyl, C 2 -C 6 -alkynyl, C 3 -C 6 -cycloalkyl, [tri-(C 1 -C 6 )-alkyldecyl]-C 2 -C 6 -alkynyl, Z 3 COR 11 , C 1 -C 6 An alkylsulfide, a monocyclic or polycyclic aromatic carbocyclic or heteroaryl group having 6 to 14 membered rings, which is monocyclic or bicyclic saturated, partially unsaturated or 3 or more ring atoms An aromatic heterocyclic ring wherein Z 3 is a bond and R 11 is hydrogen, C 1 -C 6 -alkyl or C 1 -C 6 -alkoxy; or R b and R c are each independently hydrogen, and wherein Substituents R a such as the above aliphatic, cyclic or aromatic groups may be partially or completely halogenated. 如請求項1之式I哌化合物之用途，其中R1 為氫或C1 -C6 -烷基；且其中R1 中C1 -C6 -烷基可部份或完全鹵化。As in the case of claim 1 Use of a compound wherein R 1 is hydrogen or C 1 -C 6 -alkyl; and wherein C 1 -C 6 -alkyl in R 1 may be partially or fully halogenated. 如請求項1之式I哌化合物之用途，其中R4 、R5 與R6 為氫。As in the case of claim 1 Use of a compound wherein R 4 , R 5 and R 6 are hydrogen. 如請求項1之式I哌化合物之用途，其中哌環之對掌性中心為(S)-組態。As in the case of claim 1 The use of a compound, wherein The center of the ring is the (S)-configuration. 如請求項1之式I哌化合物之用途，其中哌環之環外雙鍵為(Z)-構形。As in the case of claim 1 The use of a compound, wherein The outer double bond of the ring is in the (Z)-configuration. 一種組合物，其包含除草有效量之至少一種如請求項1至7中任一項之式I哌化合物或其農業上適用之鹽與調配作物保護劑時常用之輔助物質。A composition comprising at least one herbicidally effective amount of the formula I of any one of claims 1 to 7 A compound or an agriculturally acceptable salt thereof and an auxiliary substance commonly used in the formulation of a crop protection agent. 一種製備如請求項8之組合物之方法，其包括混合除草有效量之至少一種如請求項1至7中任一項之式I哌化合物或其農業上適用之鹽與調配作物保護劑時常用之輔助物質。A method of preparing a composition according to claim 8 which comprises mixing at least one herbicidally effective amount of the formula I according to any one of claims 1 to 7. A compound or an agriculturally acceptable salt thereof and an auxiliary substance commonly used in the formulation of a crop protection agent. 一種控制非所欲之植物生長之方法，其包括使除草有效量之至少一種如請求項1至7中任一項之式I哌化合物或其農業上適用之鹽作用在植物、其種子與/或其棲息地上。A method of controlling the growth of an unwanted plant comprising at least one herbicidally effective amount of the formula I of any one of claims 1 to 7 The compound or its agriculturally suitable salt acts on the plant, its seeds and/or its habitat. 一種製備如請求項1至7中任一項所定義通式I哌化合物之方法，其包括將式II化合物之任一醇官能基轉化為脫離基LG， 其中代號A1 、A2 、R1 、R2 、R3 、R4 、R5 、R6 、Ra 、Rb 、Rc 、Rd 、Re 與Rf 如請求項1至7中任一項中式I之定義，以形成式III化合物 其中LG為脫離基，然後自化合物III移除化合物H-LG，產生相應化合物I；或當LG為OH時，由式III化合物視情況於脫水劑之存在下脫水，產生相應之化合物I。A preparation of the formula I as defined in any one of claims 1 to 7 A method of converting a alcohol functional group of any one of the compounds of formula II to a leaving group LG, Wherein the codes A 1 , A 2 , R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R a , R b , R c , R d , R e and R f are as claimed in claims 1 to 7 Any of the definitions of formula I to form a compound of formula III Wherein LG is a leaving group and then the compound H-LG is removed from compound III to yield the corresponding compound I; or when LG is OH, the compound of formula III is optionally dehydrated in the presence of a dehydrating agent to yield the corresponding compound I. 如請求項11之方法，其中LG係選自下列各物所組成群：4-甲苯磺醯基氧、三氟甲磺醯基氧與甲磺醯基氧。 The method of claim 11, wherein the LG is selected from the group consisting of 4-toluenesulfonyloxy, trifluoromethanesulfonyloxy and methylsulfonyloxy. 如請求項11或12之方法，其中脫水劑為選自三苯基膦/偶氮二羧酸二乙酯與伯格斯試劑(Burgess reagent)系統。 The method of claim 11 or 12, wherein the dehydrating agent is selected from the group consisting of triphenylphosphine/diethyl azodicarboxylate and a Burgess reagent system.
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